Polycyclic aromatic compound

ABSTRACT

The invention provides a polycyclic aromatic compound or a salt thereof having a partial structure represented by the following general formula (I): 
     
       
         
         
             
             
         
       
     
     wherein X, ring A, ring B, ring C, and ring D are as defined in the specification.

TECHNICAL FIELD

The present invention relates to a new compound. Specifically, thepresent invention relates to a polycyclic aromatic compound including anitrogen atom, and another heteroatom or a metal atom. The presentinvention also relates to electrochemical devices, such as organicthin-film solar cells, organic thin-film transistors, and organiclight-emitting elements such as organic light-emitting diodes andorganic EL devices, including the compound.

BACKGROUND ART

Hitherto, research has been conducted on α-NPD, rubrene, Alq3, PBD, andthe like, as a luminescent material and an organic semiconductormaterial used in organic light-emitting elements such as organic ELdevices and organic light-emitting diodes (Patent Literature 1 to 3).

In an organic light-emitting element, a thin film including afluorescent organic compound or a phosphorescent organic compound issandwiched between a positive electrode and a negative electrode. Theelement utilizes light radiated when an exciton of the fluorescentcompound or the phosphorescent compound, generated through injection ofelectron or hole (positive hole) from the respective electrodes, returnsto a ground state.

Recent progresses regarding organic light-emitting elements have beenremarkable. Since the elements have characteristics enabling realizationof a lightweight and thin luminous device that has high-speed response,a diverse luminous wavelength, and high brightness when low voltage isapplied thereto, a wide range of possible applications thereof issuggested.

However, presently, the output of light with further high brightness orhigh conversion efficiency is required. In addition, there are stillmany problems regarding durability, such as changes observed over timeafter being used for a long period of time, and deterioration due tomoisture and atmosphere gas containing oxygen. Furthermore, althoughlight emission of red, green, and blue with fine color purity isrequired when considering application thereof to a full-color display orthe like, there has not been a sufficient answer for such problems.

Patent Literature 4 discloses a polycyclic aromatic compound having asingle heteroatom in a non-aromatic ring.

CITATION LIST Patent Literature

-   -   PTL 1: Japanese Unexamined Patent Publication No. 2008-171832    -   PTL 2: Japanese Unexamined Patent Publication No. 2007-027141    -   PTL 3: Japanese Unexamined Patent Publication No. 2006-004721    -   PTL 4: WO2010/53818

SUMMARY OF INVENTION Technical Problem

An object of the present invention is to provide a new polycyclicaromatic compound, and an electrochemical device including the compoundsuch as an organic thin-film solar cell, an organic thin-filmtransistor, or an organic light-emitting element.

Solution to Problem

The present inventors provide a new polycyclic aromatic compound inwhich a nitrogen atom, and another heteroatom or a metal atom (X) arearranged adjacent to each other in a non-aromatic ring; and anelectrochemical device including the compound such as an organicthin-film solar cell, an organic thin-film transistor, and an organiclight-emitting element.

Item 1. A polycyclic aromatic compound or a salt thereof having apartial structure represented by the following general formula (I).

(In the formula,

X represents B, P, P═O, P═S, P═Se, As, As═O, As═S, As═Se, Sb, Sb═O,Sb═S, Sb═Se, an optionally substituted metal in groups 3 to 11 in theperiodic table, or an optionally substituted metal or metalloid in group13 or 14 of the periodic table.

Ring A, ring B, ring C, and ring D are the same or different, and eachrepresents an optionally substituted aromatic ring or an optionallysubstituted heteroaromatic ring.)

Item 2. The polycyclic aromatic compound or a salt thereof according toitem 1, having a partial structure represented by the following generalformula (II).

(In the formula, Y^(a)s are the same or different, and each representsC— or N; or two adjacent Y^(a)s on the same ring, together with a bondtherebetween, form N—, O, S, or Se.

X represents B, P, P═O, P═S, P═Se, As, As═O, As═S, As═Se, Sb, Sb═O,Sb═S, Sb═Se, an optionally substituted metal in groups 3 to 11 in theperiodic table, or an optionally substituted metal or metalloid in group13 or 14 of the periodic table.)

Item 3. The polycyclic aromatic compound or a salt thereof according toitem 1 or 2, having a partial structure represented by the followinggeneral formula (II-1).

(In the formula,

X represents B, P, P═O, P═S, P═Se, As, As═O, As═S, As═Se, Sb, Sb═O,Sb═S, Sb═Se, an optionally substituted metal in groups 3 to 11 in theperiodic table, or an optionally substituted metal or metalloid in group13 or 14 of the periodic table.)Item 4. The polycyclic aromatic compound or a salt thereof according toany one of items 1 to 3, having a partial structure represented by anyof the following general formulae (II-2) to (II-54).

(In the formulae,

X represents B, P, P═O, P═S, P═Se, As, As═O, As═S, As═Se, Sb, Sb═O,Sb═S, Sb═Se, an optionally substituted metal in groups 3 to 11 in theperiodic table, or an optionally substituted metal or metalloid in group13 or 14 of the periodic table.

Z represents Se, S, O, or N—.)

Item 5. The polycyclic aromatic compound or a salt thereof according toany one of items 1 to 4 represented by the following general formula(II′).

(In the formula,

Ys are the same or different, and each represents CR or N; or twoadjacent Ys on the same ring, together with a bond therebetween, formNR, O, S, or Se.

X represents B, P, P═O, P═S, P═Se, As, As═O, As═S, As═Se, Sb, Sb═O,Sb═S, Sb═Se, an optionally substituted metal in groups 3 to 11 in theperiodic table, or an optionally substituted metal or metalloid in group13 or 14 of the periodic table.

R represents a hydrogen atom, halogen atom, C₁₋₂₀ alkyl group, hydroxyC₁₋₂₀ alkyl group, trifluoromethyl group, C₂₋₁₂ perfluoroalkyl group,C₃₋₈ cycloalkyl group, C₂₋₂₀ alkenyl group, C₂₋₂₀ alkynyl group, mono-or di-aryl-substituted alkenyl group, mono- or di-heteroaryl-substitutedalkenyl group, arylethynyl group, heteroarylethynyl group, hydroxygroup, C₁₋₂₀ alkoxy group, aryloxy group, trifluoromethoxy group,trifluoroethoxy group, C₂₋₁₂ perfluoroalkoxy group, C₁₋₂₀ alkylcarbonylgroup, C₁₋₂₀ alkylsulfonyl group, cyano group, nitro group, amino group,monoalkylamino group, monoarylamino group, monoheteroarylamino group,carbazole group, C₁₋₂₀ alkoxycarbonylamino group, carbamoyl group, mono-or di-alkylcarbamoyl group, sulfamoyl group, mono- or di-alkylsulfamoylgroup, C₁₋₂₀ alkylsulfonylamino group, C₁₋₂₀ alkylcarbonylamino group,aryl group, heteroaryl group, C₁₋₂₀ alkoxycarbonyl group, carboxylgroup, 5-tetrazolyl group, sulfo group (—SO₂OH), fluorosulfonyl group,SR^(a), N(R^(a))₂, B(R^(a))₂, Si(R^(a))₃, or —C≡C—Si(R^(a))₃

(wherein R^(a) represents an optionally substituted alkyl group, anoptionally substituted aryl group, or an optionally substitutedheteroaryl group; or two R^(a)s, together with an atom bound thereto,may form a bicyclic group or a tricyclic group optionally having aheteroatom);provided that the alkyl group, the alkenyl group, the alkynyl group, andthe alkoxy group are each optionally substituted with 1 to 3 atoms orgroups, selected from the group consisting of halogen atom, hydroxygroup, C₁₋₂₀ alkoxy group, aryloxy group, amino group, carbazole group,N(R^(a))₂ (wherein R^(a) is as defined above), trifluoromethyl group,C₂₋₁₂ perfluoroalkyl group, C₃₋₈ cycloalkyl group, aryl group, andheteroaryl group; and the aryl group, aryl moiety, heteroaryl group,heteroaryl moiety, and carbazole group are each optionally substitutedwith 1 to 5 atoms or groups, selected from the group consisting ofhalogen atom, C₁₋₂₀ alkyl group, hydroxy C₁₋₂₀ alkyl group,trifluoromethyl group, C₂₋₁₂ perfluoroalkyl group, C₃₋₈ cycloalkylgroup, C₂₋₂₀ alkenyl group, C₂₋₂₀ alkynyl group, mono- ordi-aryl-substituted alkenyl group, mono- or di-heteroaryl-substitutedalkenyl group, arylethynyl group, heteroarylethynyl group, hydroxygroup, C₁₋₂₀ alkoxy group, aryloxy group, trifluoromethoxy group,trifluoroethoxy group, C₂₋₁₂ perfluoroalkoxy group, cyano group, nitrogroup, amino group, carbazole group, monoalkylamino group, monoarylaminogroup, monoheteroarylamino group, N(R^(a))₂ (wherein R^(a) is as definedabove), carbamoyl group, mono- or di-alkylcarbamoyl group, sulfamoylgroup, mono- or di-alkylsulfamoyl group, C₁₋₂₀ alkylcarbonyl group,C₁₋₂₀ alkylsulfonyl group, C₁₋₂₀ alkylsulfonylamino group, C₁₋₂₀alkylcarbonylamino group, methylenedioxy group, heteroaryl group, andaryl group (wherein the aryl group is optionally substituted with 1 to 5atoms or groups, selected from the group consisting of halogen atom,C₁₋₂₀ alkyl group, C₃₋₈ cycloalkyl group, C₂₋₂₀ alkenyl group, C₂₋₂₀alkynyl group, hydroxy group, trifluoromethyl group, C₂₋₁₂perfluoroalkyl group, C₁₋₂₀ alkoxy group, aryloxy group,trifluoromethoxy group, trifluoroethoxy group, C₂₋₁₂ perfluoroalkoxygroup, C₁₋₂₀ alkylcarbonyl group, C₁₋₂₀ alkylsulfonyl group,methylenedioxy group, cyano group, nitro group, amino group, carbazolegroup, and N(R^(a))₂ (wherein R^(a) is as defined above)).

Or, two adjacent Rs, together with carbon atom bound thereto, form afive- or six-membered monocyclic group, bicyclic group, or tricyclicgroup optionally having a heteroatom; or three adjacent Rs form,together with carbon atom bound thereto, a bicyclic group or a tricyclicgroup optionally having a heteroatom.

When two adjacent Rs are Rs in adjacent rings, the two Rs form a singlebond, CH₂, CHR^(a), CR^(a) ₂, NR^(a), Si(R^(a))₂, BR^(a) (wherein R^(a)is as defined above), Se, S, or O.)

Item 6. The polycyclic aromatic compound or a salt thereof according toany one of items 1 to 5 represented by the following general formula(II′-1).

(In the formula,

X represents B, P, P═O, P═S, P═Se, As, As═O, As═S, As═Se, Sb, Sb═O,Sb═S, Sb═Se, an optionally substituted metal in groups 3 to 11 in theperiodic table, or an optionally substituted metal or metalloid in group13 or 14 of the periodic table.

R represents a hydrogen atom, halogen atom, C₁₋₂₀ alkyl group, hydroxyC₁₋₂₀ alkyl group, trifluoromethyl group, C₂₋₁₂ perfluoroalkyl group,C₃₋₈ cycloalkyl group, C₂₋₂₀ alkenyl group, C₂₋₂₀ alkynyl group, mono-or di-aryl-substituted alkenyl group, mono- or di-heteroaryl-substitutedalkenyl group, arylethynyl group, heteroarylethynyl group, hydroxygroup, C₁₋₂₀ alkoxy group, aryloxy group, trifluoromethoxy group,trifluoroethoxy group, C₂₋₁₂ perfluoroalkoxy group, C₁₋₂₀ alkylcarbonylgroup, C₁₋₂₀ alkylsulfonyl group, cyano group, nitro group, amino group,monoalkylamino group, monoarylamino group, monoheteroarylamino group,carbazole group, C₁₋₂₀ alkoxycarbonylamino group, carbamoyl group, mono-or di-alkylcarbamoyl group, sulfamoyl group, mono- or di-alkylsulfamoylgroup, C₁₋₂₀ alkylsulfonylamino group, C₁₋₂₀ alkylcarbonylamino group,aryl group, heteroaryl group, C₁₋₂₀ alkoxycarbonyl group, carboxylgroup, 5-tetrazolyl group, sulfo group (—SO₂OH), fluorosulfonyl group,SR^(a), N(R^(a))₂, B(R^(a))₂, Si(R^(a))₃, or —C≡C—Si(R^(a))₃ (whereinR^(a) represents an optionally substituted alkyl group, an optionallysubstituted aryl group, or an optionally substituted heteroaryl group;or two R^(a)s, together with an atom bound thereto, may form a bicyclicgroup or a tricyclic group optionally having a heteroatom);

provided that the alkyl group, the alkenyl group, the alkynyl group, andthe alkoxy group are each optionally substituted with 1 to 3 atoms orgroups, selected from the group consisting of halogen atom, hydroxygroup, C₁₋₂₀ alkoxy group, aryloxy group, amino group, carbazole group,N(R^(a))₂ (wherein R^(a) is as defined above), trifluoromethyl group,C₂₋₁₂ perfluoroalkyl group, C₃₋₈ cycloalkyl group, aryl group, andheteroaryl group; andthe aryl group, aryl moiety, heteroaryl group, heteroaryl moiety, andcarbazole group are each optionally substituted with 1 to 5 atoms orgroups, selected from the group consisting of halogen atom, C₁₋₂₀ alkylgroup, hydroxy C₁₋₂₀ alkyl group, trifluoromethyl group, C₂₋₁₂perfluoroalkyl group, C₃₋₈ cycloalkyl group, C₂₋₂₀ alkenyl group, C₂₋₂₀alkynyl group, mono- or di-aryl-substituted alkenyl group, mono- ordi-heteroaryl-substituted alkenyl group, arylethynyl group,heteroarylethynyl group, hydroxy group, C₁₋₂₀ alkoxy group, aryloxygroup, trifluoromethoxy group, trifluoroethoxy group, C₂₋₁₂perfluoroalkoxy group, cyano group, nitro group, amino group, carbazolegroup, monoalkylamino group, monoarylamino group, monoheteroarylaminogroup, N(R^(a))₂ (wherein R^(a) is as defined above), carbamoyl group,mono- or di-alkylcarbamoyl group, sulfamoyl group, mono- ordi-alkylsulfamoyl group, C₁₋₂₀ alkylcarbonyl group, C₁₋₂₀ alkylsulfonylgroup, C₁₋₂₀ alkylsulfonylamino group, C₁₋₂₀ alkylcarbonylamino group,methylenedioxy group, heteroaryl group, and aryl group (wherein the arylgroup is optionally substituted with 1 to 5 atoms or groups, selectedfrom the group consisting of halogen atom, C₁₋₂₀ alkyl group, C₃₋₈cycloalkyl group, C₂₋₂₀ alkenyl group, C₂₋₂₀ alkynyl group, hydroxygroup, trifluoromethyl group, C₂₋₁₂ perfluoroalkyl group, C₁₋₂₀ alkoxygroup, aryloxy group, trifluoromethoxy group, trifluoroethoxy group,C₂₋₁₂ perfluoroalkoxy group, C₁₋₂₀ alkylcarbonyl group, C₁₋₂₀alkylsulfonyl group, methylenedioxy group, cyano group, nitro group,amino group, carbazole group, and N(R^(a))₂ (wherein R^(a) is as definedabove)).

Or, two adjacent Rs, together with carbon atom bound thereto, form afive- or six-membered monocyclic group, bicyclic group, or tricyclicgroup optionally having a heteroatom; or three adjacent Rs form,together with carbon atom bound thereto, a bicyclic group or a tricyclicgroup optionally having a heteroatom.

When two adjacent Rs are Rs in adjacent rings, the two Rs form a singlebond, CH₂, CHR^(a), CR^(a) ₂, NR^(a), Si(R^(a))₂, BR^(a) (wherein R^(a)is as defined above), Se, S, or O.)

Item 7. The polycyclic aromatic compound or a salt thereof according toany one of items 1 to 6 represented by the following general formulae(III′) to (XXIII′).

(In the formulae,

Ys are the same or different, and each represents CR or N; or twoadjacent Ys on the same ring, together with a bond therebetween, formNR, O, S, or Se.

X represents B, P, P═O, P═S, P═Se, As, As═O, As═S, As═Se, Sb, Sb═O,Sb═S, Sb═Se, an optionally substituted metal in groups 3 to 11 in theperiodic table, or an optionally substituted metal or metalloid in group13 or 14 of the periodic table.

R represents a hydrogen atom, halogen atom, C₁₋₂₀ alkyl group, hydroxyC₁₋₂₀ alkyl group, trifluoromethyl group, C₂₋₁₂ perfluoroalkyl group,C₃₋₈ cycloalkyl group, C₂₋₂₀ alkenyl group, C₂₋₂₀ alkynyl group, mono-or di-aryl-substituted alkenyl group, mono- or di-heteroaryl-substitutedalkenyl group, arylethynyl group, heteroarylethynyl group, hydroxygroup, C₁₋₂₀ alkoxy group, aryloxy group, trifluoromethoxy group,trifluoroethoxy group, C₂₋₁₂ perfluoroalkoxy group, C₁₋₂₀ alkylcarbonylgroup, C₁₋₂₀ alkylsulfonyl group, cyano group, nitro group, amino group,monoalkylamino group, monoarylamino group, monoheteroarylamino group,carbazole group, C₁₋₂₀ alkoxycarbonylamino group, carbamoyl group, mono-or di-alkylcarbamoyl group, sulfamoyl group, mono- or di-alkylsulfamoylgroup, C₁₋₂₀ alkylsulfonylamino group, C₁₋₂₀ alkylcarbonylamino group,aryl group, heteroaryl group, C₁₋₂₀ alkoxycarbonyl group, carboxylgroup, 5-tetrazolyl group, sulfo group (—SO₂OH), fluorosulfonyl group,SR^(a), N(R^(a))₂, B(R^(a))₂, Si(R^(a))₃, or —C≡C—Si(R^(a))₃ (whereinR^(a) represents an optionally substituted alkyl group, an optionallysubstituted aryl group, or an optionally substituted heteroaryl group;or two R^(a)s, together with an atom bound thereto, may form a bicyclicgroup or a tricyclic group optionally having a heteroatom);

provided that the alkyl group, the alkenyl group, the alkynyl group, andthe alkoxy group are each optionally substituted with 1 to 3 atoms orgroups, selected from the group consisting of halogen atom, hydroxygroup, C₁₋₂₀ alkoxy group, aryloxy group, amino group, carbazole group,N(R^(a))₂ (wherein R^(a) is as defined above), trifluoromethyl group,C₂₋₁₂ perfluoroalkyl group, C₃₋₈ cycloalkyl group, aryl group, andheteroaryl group; andthe aryl group, aryl moiety, heteroaryl group, heteroaryl moiety, andcarbazole group are each optionally substituted with 1 to 5 atoms orgroups, selected from the group consisting of halogen atom, C₁₋₂₀ alkylgroup, hydroxy C₁₋₂₀ alkyl group, trifluoromethyl group, C₂₋₁₂perfluoroalkyl group, C₃₋₈ cycloalkyl group, C₂₋₂₀ alkenyl group, C₂₋₂₀alkynyl group, mono- or di-aryl-substituted alkenyl group, mono- ordi-heteroaryl-substituted alkenyl group, arylethynyl group,heteroarylethynyl group, hydroxy group, C₁₋₂₀ alkoxy group, aryloxygroup, trifluoromethoxy group, trifluoroethoxy group, C₂₋₁₂perfluoroalkoxy group, cyano group, nitro group, amino group, carbazolegroup, monoalkylamino group, monoarylamino group, monoheteroarylaminogroup, N(R^(a))₂ (wherein R^(a) is as defined above), carbamoyl group,mono- or di-alkylcarbamoyl group, sulfamoyl group, mono- ordi-alkylsulfamoyl group, C₁₋₂₀ alkylcarbonyl group, C₁₋₂₀ alkylsulfonylgroup, C₁₋₂₀ alkylsulfonylamino group, C₁₋₂₀ alkylcarbonylamino group,methylenedioxy group, heteroaryl group, and aryl group (wherein the arylgroup is optionally substituted with 1 to 5 atoms or groups, selectedfrom the group consisting of halogen atom, C₁₋₂₀ alkyl group, C₃₋₈cycloalkyl group, C₂₋₂₀ alkenyl group, C₂₋₂₀ alkynyl group, hydroxygroup, trifluoromethyl group, C₂₋₁₂ perfluoroalkyl group, C₁₋₂₀ alkoxygroup, aryloxy group, trifluoromethoxy group, trifluoroethoxy group,C₂₋₁₂ perfluoroalkoxy group, C₁₋₂₀ alkylcarbonyl group, C₁₋₂₀alkylsulfonyl group, methylenedioxy group, cyano group, nitro group,amino group, carbazole group, and N(R^(a))₂ (wherein R^(a) is as definedabove)).

Or, two adjacent Rs, together with carbon atom bound thereto, form afive- or six-membered monocyclic group, bicyclic group, or tricyclicgroup optionally having a heteroatom; or three adjacent Rs form,together with carbon atom bound thereto, a bicyclic group or a tricyclicgroup optionally having a heteroatom.

When two adjacent Rs are Rs in adjacent rings, the two Rs form a singlebond, CH₂, CHR^(a), CR^(a) ₂, NR^(a), Si(R^(a))₂, BR^(a) (wherein R^(a)is as defined above), Se, S, or O.)

Item 8. The compound according to any one of items 1 to 7 represented byany one of the following formulae (II′-1A) to (XIV′-1A).

(In the formulae,

X represents B, P, P═O, P═S, P═Se, As, As═O, As═S, As═Se, Sb, Sb═O,Sb═S, Sb═Se, an optionally substituted metal in groups 3 to 11 in theperiodic table, or an optionally substituted metal or metalloid in group13 or 14 of the periodic table.

R represents a hydrogen atom, halogen atom, C₁₋₂₀ alkyl group, hydroxyC₁₋₂₀ alkyl group, trifluoromethyl group, C₂₋₁₂ perfluoroalkyl group,C₃₋₈ cycloalkyl group, C₂₋₂₀ alkenyl group, C₂₋₂₀ alkynyl group, mono-or di-aryl-substituted alkenyl group, mono- or di-heteroaryl-substitutedalkenyl group, arylethynyl group, heteroarylethynyl group, hydroxygroup, C₂₋₂₀ alkoxy group, aryloxy group, trifluoromethoxy group,trifluoroethoxy group, C₂₋₁₂ perfluoroalkoxy group, C₁₋₂₀ alkylcarbonylgroup, C₂₋₂₀ alkylsulfonyl group, cyano group, nitro group, amino group,monoalkylamino group, monoarylamino group, monoheteroarylamino group,carbazole group, C₁₋₂₀ alkoxycarbonylamino group, carbamoyl group, mono-or di-alkylcarbamoyl group, sulfamoyl group, mono- or di-alkylsulfamoylgroup, C₁₋₂₀ alkylsulfonylamino group, C₁₋₂₀ alkylcarbonylamino group,aryl group, heteroaryl group, C₁₋₂₀ alkoxycarbonyl group, carboxylgroup, 5-tetrazolyl group, sulfo group (—SO₂OH), fluorosulfonyl group,SR^(a), N(R^(a))₂, B(R^(a))₂, Si(R^(a))₃, or —C≡C—Si(R^(a))₃

(wherein R^(a) represents an optionally substituted alkyl group, anoptionally substituted aryl group, or an optionally substitutedheteroaryl group; or two R^(a)s, together with an atom bound thereto,may form a bicyclic group or a tricyclic group optionally having aheteroatom);Provided that the alkyl group, the alkenyl group, the alkynyl group, andthe alkoxy group are each optionally substituted with 1 to 3 atoms orgroups, selected from the group consisting of halogen atom, hydroxygroup, C₁₋₂₀ alkoxy group, aryloxy group, amino group, carbazole group,N(R^(a))₂ (wherein R^(a) is as defined above), trifluoromethyl group,C₂₋₁₂ perfluoroalkyl group, C₃₋₈ cycloalkyl group, aryl group, andheteroaryl group; and the aryl group, aryl moiety, heteroaryl group,heteroaryl moiety, and carbazole group are each optionally substitutedwith 1 to 5 atoms or groups, selected from the group consisting ofhalogen atom, C₁₋₂₀ alkyl group, hydroxy C₁₋₂₀ alkyl group,trifluoromethyl group, C₂₋₁₂ perfluoroalkyl group, C₃₋₈ cycloalkylgroup, C₂₋₂₀ alkenyl group, C₂₋₂₀ alkynyl group, mono- ordi-aryl-substituted alkenyl group, mono- or di-heteroaryl-substitutedalkenyl group, arylethynyl group, heteroarylethynyl group, hydroxygroup, C₁₋₂₀ alkoxy group, aryloxy group, trifluoromethoxy group,trifluoroethoxy group, C₂₋₁₂ perfluoroalkoxy group, cyano group, nitrogroup, amino group, carbazole group, monoalkylamino group, monoarylaminogroup, monoheteroarylamino group, N(R^(a))₂ (wherein R^(a) is as definedabove), carbamoyl group, mono- or di-alkylcarbamoyl group, sulfamoylgroup, mono- or di-alkylsulfamoyl group, C₁₋₂₀ alkylcarbonyl group,C₁₋₂₀ alkylsulfonyl group, C₁₋₂₀ alkylsulfonylamino group, C₁₋₂₀alkylcarbonylamino group, methylenedioxy group, heteroaryl group, andaryl group (wherein the aryl group is optionally substituted with 1 to 5atoms or groups, selected from the group consisting of halogen atom,C₁₋₂₀ alkyl group, C₃₋₈ cycloalkyl group, C₂₋₂₀ alkenyl group, C₂₋₂₀alkynyl group, hydroxy group, trifluoromethyl group, C₂₋₁₂perfluoroalkyl group, C₁₋₂₀ alkoxy group, aryloxy group,trifluoromethoxy group, trifluoroethoxy group, C₂₋₁₂ perfluoroalkoxygroup, C₁₋₂₀ alkylcarbonyl group, C₁₋₂₀ alkylsulfonyl group,methylenedioxy group, cyano group, nitro group, amino group, carbazolegroup, and N(R^(a))₂ (wherein R^(a) is as defined above)).

Or, two adjacent Rs, together with carbon atom bound thereto, form afive- or six-membered monocyclic group, bicyclic group, or tricyclicgroup optionally having a heteroatom; or three adjacent Rs form,together with a carbon atom bound thereto, a bicyclic group or atricyclic group optionally having a heteroatom.

When two adjacent Rs are Rs in adjacent rings, the two Rs form a singlebond, CH₂, CHR^(a), CR^(a) ₂, NR^(a), Si(R^(a))₂, BR^(a) (wherein R^(a)is as defined above), Se, S, or O.)

Item 9. An electrochemical device containing the compound according toany one of items 1 to 8.Item 10. The electrochemical device according to item 9, wherein thedevice is an organic light-emitting element, an organic thin-filmtransistor, or an organic thin-film solar cell.

Advantageous Effects of Invention

The present invention can provide a new compound for electrontransporting materials, luminescent materials, positive holetransporting materials, and the like, suitable to be used in organicthin-film solar cells, organic thin-film transistors, and organiclight-emitting elements such as organic EL devices and organiclight-emitting diodes.

DESCRIPTION OF EMBODIMENTS

In the present specification, Y^(a)s are the same or different, and eachrepresents C— or N; or two adjacent Y^(a)s on the same ring, togetherwith a bond therebetween, form N—, O, S, or Se. Furthermore, Ys are thesame or different, and form C—R or N; or two adjacent Ys on the samering, together with a bond therebetween, form NR, O, S, or Se. AlthoughY and Y^(a) are groups corresponding to each other, Y^(a) is used in apartial structure, and does not include an R group.

The present invention provides a polycyclic aromatic compound or a saltthereof having a partial structure represented by the following generalformula (I).

(In the formula, X, ring A, ring B, ring C, and ring D are as definedabove.)

One preferable embodiment of the present invention is the polycyclicaromatic compound or a salt thereof having a partial structurerepresented by the following general formula (II).

(In the formula, X and Y^(a) are as defined above.)

One preferable embodiment of the present invention is the polycyclicaromatic compound or a salt thereof having a partial structurerepresented by the following general formula (II-1).

(In the formula, X is as defined above.)

Another preferable embodiment of the present invention is the polycyclicaromatic compound or a salt thereof having a partial structurerepresented by any one of the following general formulae (II-2) to(II-54).

(In the formulae, X and Z are as defined above.)

Examples of the compound having the partial structure represented bygeneral formula (I) include compounds having a skeleton of the following1 to 149 (these compounds are further optionally substituted).

(In the formulae, X and Z are as defined above.)

Examples of metals in groups 3 to 11 of the periodic table and metals ormetalloids in group 13 or 14 of the periodic table, represented by X,include those described below.

Group 3: Sc, Y, lanthanoid

Group 4: Ti, Zr, Hf Group 5: V, Nb, Ta Group 6: Cr, Mo, W Group 7: Mn,Tc, Re Group 8: Fe, Ru, Os Group 9: Co, Rh, Ir Group 10: Ni, Pd, PtGroup 11: Cu, Ag, Au Group 13: Al, Ga, In, Tl Group 14: Si, Ge, Sn, Pb

The metals in groups 3 to 11 of the periodic table and the metals ormetalloids in group 13 or 14 of the periodic table, represented by X,are each optionally substituted. Here, “optionally substituted” meansthat the metals or metalloids may include 0 to 3 substituent groups R(wherein R is as defined above), or 0 to 3 neutral ligands R¹.

Examples of neutral ligands R¹ include aromatic compounds having anitrogen atom as a ring atom, such as pyridine, bipyridine,phenanthroline, terpyridine, imidazole, pyrimidine, pyrazine, quinoline,isoquinoline, and acridine; and derivatives thereof. However, when X hasboth R and R¹, R and R¹ may form a single compound (8-hydroxyquinoline),as in the following Case (3).

For example, a compound having a neutral ligand R¹ can be produced inthe following manner.

(In the formulae, (R) indicates that R¹ is the R group defined above,and (R¹) indicates that R¹ is a neutral ligand.)

Case (1) represents a case where a neutral ligand (R¹) binds to X (metalor metalloid) of (I) to obtain compound (I′).

Case (2) represents a case where a neutral ligand (R) further binds to(I″) in which R═Cl and X (metal or metalloid) is substituted with the Rgroup, to obtain compound (I′″).

Case (3) represents a method for obtaining compound (I″″) having (R) and(R), by causing 8-hydroxyquinoline to act on (I″) in which R═Cl and X(metal or metalloid) is substituted with the R group, to substitute Cl,which is the R group, with an oxygen atom of a phenolic hydroxyl group;and to simultaneously cause coordination of an endocyclic N atom (R¹group) of quinoline, which is a neutral ligand.

A compound having a neutral ligand can be easily produced by thoseskilled in the art by referring to Case (1) to Case (3).

X₁ can be changed to X₂ in a manner similar to that described below.

X₁ and X₂ can be changed when the electronegativities thereof are aboutthe same as, or are, X₁<X₂. For example, when X₁=Ge—R, X₂ can be changedas B, P, P═O, P═S, P═Se, As, As═O, As═S, As═Se, Sb, Sb═O, Sb═S, Sb═Se,Mo, W, Ru, Os, Rh, Ir, Pd, Pt, Au, or Pb (these metals are optionallysubstituted). As the changing method, with respect to compound (IA)having X₁, 1 mol to an excessive amount of a halide, an alkoxyderivative, an aryloxy derivative, an acyloxy derivative, or a haloaminoderivative of X₂, 0 mole to an excessive amount of a Lewis acid, 0 moleto an excessive amount of a base are added and allowed to react bystirring for 30 minutes to 24 hours at a temperature of room temperatureto about 250° C. in a solvent or under a non-solvent condition to obtaincompound (IB) having X₂.

Examples of the solvents that can be used include anhydrous ethersolvents such as anhydrous diethyl ether, anhydrous THF, and anhydrousdibutyl ether; aromatic hydrocarbon solvents such as benzene, toluene,xylene, and mesitylene; aromatic halide-based solvents such aschlorobenzene and 1,2-dichlorobenzene; and the like.

Examples of the Lewis acid that can be used include AlCl₃, AlBr₃,BF₃.OEt₂, BCl₃, BBr₃, GaCl₃, GaBr₃, InCl₃, InBr₃, In(OTf)₃, SnCl₄,SnBr₄, AgOTf, Sc(OTf)₃, ZnCl₂, ZnBr₂, Zn(OTf)₂, MgCl₂, MgBr₂, Mg(OTf)₂,and the like.

Examples of the base that can be used include diisopropylethylamine,2,2,6,6,-tetra methyl piperidine, 1,2,2,6,6,-pentamethylpiperidine,2,4,6-collidine, 2,6-lutidine, triethylamine, triisobutylamine, and thelike.

When X₂═P, a compound in which X₂ is P═S can be directly obtained byconducting the reaction that uses the Lewis acid and the base in thepresence of sulfur (S8).

A compound having bound thereto a sulfur atom can also be similarlyobtained when X₂ is other elements such as As and Sb.

Although a description of the compound having the partial structure ofgeneral formula (I) has been provided above, a neutral ligand can beintroduced, and a conversion of X₁ to X₂ is similarly possible, withcompounds of general formulae (II) to (XIVA); compounds of generalformulae (II-1) to (II-54), compounds of general formulae (II′) to(XXIII′); compounds of general formulae (II′-1) to (XIV′-1A); andcompounds of 1 to 149.

Examples of preferable X group include B, P, P═O, P═S, Si—R, Ge—R, Ga,Pt, Ru, Ir, Au, and the like.

As described herein, “two adjacent Y^(a)s on the same ring, togetherwith a bond therebetween, form N—, O, S, or Se” means that when adjacentY^(a)s are bound with a double bond, such as Y^(a)═Y^(a), Y^(a)═Y^(a)can be N—, O, S, or Se; and when adjacent Y^(a)s are bound with a singlebond, such as Y^(a)—Y^(a), a structure shown in the following formulaecan be obtained:

(in the formulae, Y^(a) is as defined above).

The term “two adjacent Ys on the same ring, together with a bondtherebetween, form NR, O, S, or Se” has the same meaning.

In the present specification, “adjacent R groups” may be adjacent groupson the same ring, or the closest R groups each existing on adjacentrings.

Examples of aromatic rings described as “an optionally substitutedaromatic ring” include a benzene ring, naphthalene ring, azulene ring,biphenylene ring, fluorene ring, anthracene ring, indacene ring,phenanthrene ring, phenalene ring, pyrene ring, chrysene ring,triphenylene ring, fluoranthene ring, acephenanthrylene ring,aceanthrylene ring, picene ring, naphthacene ring, perylene ring,acenaphthylene ring, acenaphthene ring, indane ring, indene ring, andtetrahydronaphthalene ring.

Examples of heteroaromatic rings described as “an optionally substitutedheteroaromatic ring” include a furan ring, thiophene ring, selenophenering, pyrrole ring, imidazole ring, triazole ring, isothiazole ring,oxazole ring, isoxazole ring, triazole ring, borole ring, phospholering, silole ring, azaborine ring, pyridine ring, pyrimidine ring,triazine ring, pyran ring, indole ring, isoindole ring, quinoline ring,isoquinoline ring, quinoxaline ring, benzoxazole ring, benzothiazolering, benzisoxazole ring, benzisothiazole ring, benzofuran ring,benzothiophene ring, benzopyran ring, benzimidazole ring, benzoborolering, benzophosphole ring, benzosilole ring, benzazaborine ring,carbazole ring, indolizine ring, acridine ring, phenazine ring,phenanthridine ring, phenanthroline ring, phenoxazine ring,phenothiazine ring, benzoselenophene ring, naphthofuran ring,naphthoxazole ring, naphthothiazole ring, naphthoisoxazole ring,naphthoimidazole ring, naphthoborole ring, naphthophosphole ring,naphthosilole ring, naphthoazaborine ring, naphthopyran ring,benzoindole ring, benzisoindole ring, benzoquinoline ring,benzisoquinoline ring, benzoquinoxaline ring, and those in the followingformulae:

(in the formulae, R^(a) is as defined above).

The number of substituent groups of an optionally substituted aromaticring or an optionally substituted heteroaromatic ring is 1 to 4, andpreferably 1, 2, or 3. Examples of the substituent group of anoptionally substituted aromatic ring or an optionally substitutedheteroaromatic ring include groups represented by R.

Examples of “a five- or six-membered monocyclic group, bicyclic group,or tricyclic group optionally having a heteroatom” include benzene,naphthalene, azulene, biphenylene, fluorene, anthracene, indacene,phenanthrene, phenalene, acenaphthylene, acenaphthene, indane, indene,tetrahydronaphthalene, cyclopentadiene, cyclohexadiene, furan,thiophene, selenophene, pyrrole, imidazole, triazole, isothiazole,oxazole, isoxazole, triazole, borole, phosphole, silole, azaborine,pyridine, pyrimidine, triazine, pyran, indole, isoindole, quinoline,isoquinoline, quinoxaline, benzoxazole, benzothiazole, benzisoxazole,benzisothiazole, benzofuran, benzothiophene, benzopyran, benzimidazole,benzoborole, benzophosphole, benzosilole, benzazaborine, indolizine,acridine, phenazine, phenanthridine, phenanthroline, benzoselenophene,naphthofuran, naphthoxazole, naphthothiazole, naphthoisoxazole,naphthoimidazole, naphthoborole, naphthophosphole, naphthosilole,naphthoazaborine, naphthopyran, benzoindole, benzisoindole,benzoquinoline, benzisoquinoline, benzoquinoxaline, those in thefollowing formulae:

(in the formulae, R^(a) is as defined above), or a five- or six-memberedring group having X group.

Examples of “a bicyclic group or a tricyclic group optionally having aheteroatom” include naphthalene, azulene, biphenylene, fluorene,anthracene, indacene, phenanthrene, phenalene, acenaphthylene,acenaphthene, indane, indene, tetrahydronaphthalene, indole, isoindole,quinoline, isoquinoline, quinoxaline, benzoxazole, benzothiazole,benzisoxazole, benzisothiazole, benzofuran, benzothiophene, benzopyran,benzimidazole, benzoborole, benzophosphole, benzosilole, benzazaborine,indolizine, acridine, phenazine, phenanthridine, phenanthroline,benzoselenophene, naphthofuran, naphthoxazole, naphthothiazole,naphthoisoxazole, naphthoimidazole, naphthoborole, naphthophosphole,naphthosilole, naphthoazaborine, naphthopyran, benzoindole,benzisoindole, benzoquinoline, benzisoquinoline, benzoquinoxaline, andthose in the following formulae:

(in the formulae, R^(a) is as defined above).

In the present specification, although the number of carbon atoms isspecified as “C₁₋₂₀ alkylcarbonyl,” this number of carbon atoms onlymodifies the group or moiety that immediately follows. Thus, in theabove-described case, since C₁₋₂₀ only modifies alkyl, “C₁alkylcarbonyl” corresponds to acetyl.

Alkyl groups and alkyl moieties may be linear or branched.

In the present specification, an alkyl moiety not only includesrespective alkyl groups of an optionally substituted alkyl group, C₁₋₂₀alkylsulfonyl group, C₁₋₂₀ alkylsulfonylamino group, C₁₋₂₀alkylcarbonylamino group, and C₁₋₂₀ alkylcarbonyl group, but alsoincludes an alkyl group of a monoalkylamino group, a mono- ordi-alkylsulfamoyl group, and a mono- or di-alkylcarbamoyl group.

An aryl moiety refers to an aryl group of a mono- or di-aryl-substitutedalkenyl group, arylethynyl group, aryloxy group, monoarylamino group, oran optionally substituted aryl group.

A heteroaryl moiety refers to a heteroaryl group of amonoheteroarylamino group, mono- or heteroaryl-substituted alkenylgroup, heteroarylethynyl group, or an optionally substituted heteroarylgroup.

Although “halogen atom” refers to fluorine, chlorine, bromine, oriodine, fluorine, chlorine, and bromine are preferable.

The “C₁₋₂₀ alkyl group” may be linear, branched, or cyclic; and is, forexample, a C₁₋₂₀ alkyl group such as methyl group, ethyl group, n-propylgroup, isopropyl group, n-butyl group, isobutyl group, tert-butyl group,n-pentyl group, isopentyl group, hexyl group, heptyl group, octyl group,nonyl group, decyl group, undecyl group, dodecyl group, tetradecylgroup, hexadecyl group, octadecyl group, and eicosyl group, preferably aC₁₋₁₀ alkyl group, and more preferably a C₁₋₆ alkyl group.

Examples of the “C₃₋₈ cycloalkyl group” include cyclopropyl group,cyclobutyl group, cyclopentyl group, cyclohexyl group and cycloheptylgroup, and cyclooctyl group.

The “C₂₋₂₀ alkenyl group” may be linear, branched, or cyclic; and refersto one that has at least one double bond. Examples thereof include vinylgroup, allyl group, 1-propenyl group, 2-methyl-2-propenyl group,isopropenyl group, 1-, 2-, or 3-butenyl group, 2-, 3-, or 4-pentenylgroup, 2-methyl-2-butenyl group, 3-methyl-2-butenyl group, 5-hexenylgroup, 1-cyclopentenyl group, 1-cyclohexenyl group, and3-methyl-3-butenyl group, preferably a C₂₋₁₂ alkenyl group, and morepreferably a C₂₋₆ alkenyl group.

The “C₂₋₂₀ alkynyl group” may be linear, branched, or cyclic; and refersto one that has at least one triple bond. Examples thereof includeethynyl group, 1- or 2-propynyl group, 1-, 2-, or 3-butynyl group,1-methyl-2-propynyl group, 1-pentynyl group, 1-hexynyl group, 1-heptynylgroup, 1-octynyl group, 1-nonenyl group, 1-decynyl group, 1-undecenylgroup, and 1-dodecynyl group, preferably a C₂₋₁₀ alkynyl group, and morepreferably a C₂₋₆ alkynyl group.

The “hydroxy C₁₋₂₀ alkyl group” may be linear or branched; and is, forexample, a hydroxy C₁₋₂₀ alkyl group such as hydroxymethyl group,hydroxyethyl group, hydroxy n-propyl group, hydroxyisopropyl group,hydroxy n-butyl group, hydroxyisobutyl group, hydroxy tert-butyl group,hydroxy n-pentyl group, hydroxyisopentyl group, hydroxyhexyl group,hydroxyheptyl group, hydroxyoctyl group, hydroxynonyl group,hydroxydecyl group, hydroxyundecyl group, hydroxydodecyl group,hydroxytetradecyl group, hydroxyhexadecyl group, hydroxyoctadecyl group,and hydroxyeicosyl group, preferably a hydroxy C₁₋₁₀ alkyl group, andmore preferably a hydroxy C₁₋₆ alkyl group.

The “C₁₋₂₀ alkoxy group” may be linear or branched; and is, for example,a C₁₋₂₀ alkoxy group such as methoxy group, ethoxy group, propoxy group,isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group,pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group,octyloxy group, nonyloxy group, decyloxy group, undecyloxy group,dodecyloxy group, tetradecyloxy group, hexadecyloxy group, octadecyloxygroup, and eicosyloxy group, preferably a C₁₋₁₀ alkoxy group, and morepreferably a C₁₋₆ alkoxy group.

As a trifluoroethoxy group, CF₃CH₂O— is preferable.

The “C₂₋₁₂ perfluoroalkyl group” may be linear or branched; and is, forexample, a C₂₋₁₂ perfluoroalkyl group such as perfluoroethyl group,perfluoro n-propyl group, perfluoroisopropyl group, perfluoro n-butylgroup, perfluoroisobutyl group, perfluoro tert-butyl group, perfluoron-pentyl group, perfluoroisopentyl group, perfluorohexyl group,perfluoroheptyl group, perfluorooctyl group, perfluorononyl group,perfluorodecyl group, and perfluoroundecyl group, preferably a C₂₋₁₀perfluoroalkyl group, and more preferably a C₂₋₆ perfluoroalkyl group.

The “C₂₋₁₂ perfluoroalkoxy group” may be linear or branched; and is, forexample, a C₂₋₁₂ perfluoroalkoxy group such as perfluoroethoxy group,perfluoro n-propyloxy group, perfluoroisopropyloxy group, perfluoron-butoxy group, perfluoroisobutoxy group, perfluoro tert-butoxy group,perfluoro n-pentyloxy group, perfluoroisopentyloxy group,perfluorohexyloxy group, perfluoroheptyloxy group, perfluorooctyloxygroup, perfluorononyloxy group, perfluorodecyloxy group, andperfluoroundecyloxy group, preferably a C₂₋₁₀ perfluoroalkoxy group, andmore preferably a C₂₋₆ perfluoroalkoxy group.

In a monoalkylamino group, mono- or di-alkylcarbamoyl group, or mono- ordi-alkylsulfamoyl group, “monoalkyl” refers to one hydrogen atom boundto a nitrogen atom of an amino group, carbamoyl group, or sulfamoylgroup, being substituted with a C₁₋₂₀ alkyl; and “dialkyl” refers to twohydrogen atoms bound to a nitrogen atom of an amino group, carbamoylgroup, or sulfamoyl group, being substituted with the same or differentC₁₋₂₀ alkyl, or being substituted with a three- to eight-membered,preferably five- or six-membered, nitrogen-containing cyclic group.

Nitrogen-containing cyclic group refers to morpholino group,1-pyrrolidinyl group, piperidino, and 4-methyl-1-piperazinyl group.

Examples of the monoalkylamino group include amino group that ismono-substituted with a C₁₋₂₀ alkyl group, such as methylamino group,ethylamino group, n-propylamino group, isopropylamino group,n-butylamino group, isobutylamino group, tert-butylamino group,n-pentylamino group, isopentylamino group, and hexylamino group,preferably a C₁₋₁₀ alkyl group, and more preferably a C₁₋₆ alkyl group.

Examples of the monoalkylcarbamoyl group include carbamoyl that ismono-substituted with a C₁₋₂₀ alkyl group such as methylcarbamoyl group,ethylcarbamoyl group, n-propylcarbamoyl group, isopropylcarbamoyl group,n-butylcarbamoyl group, isobutylcarbamoyl group, tert-butylcarbamoylgroup, n-pentylcarbamoyl group, isopentylcarbamoyl group, andhexylcarbamoyl group, preferably a C₁₋₁₀ alkyl group, and morepreferably a C₁₋₆ alkyl group.

Examples of a dialkylcarbamoyl group include carbamoyl that isdi-substituted with a C₁₋₂₀ alkyl group such as dimethylcarbamoyl group,diethylcarbamoyl group, di-n-propylcarbamoyl group, diisopropylcarbamoylgroup, di-n-butylcarbamoyl group, diisobutylcarbamoyl group,di-tert-butylcarbamoyl group, di-n-pentylcarbamoyl group,diisopentylcarbamoyl group, and dihexylcarbamoyl group, preferably aC₁₋₁₀ alkyl group, and more preferably a C₁₋₆ alkyl group.

Examples of the monoalkylsulfamoyl group include sulfamoyl that ismono-substituted with a C₁₋₂₀ alkyl group such as methylsulfamoyl group,ethylsulfamoyl group, n-propylsulfamoyl group, isopropylsulfamoyl group,n-butylsulfamoyl group, isobutylsulfamoyl group, tert-butylsulfamoylgroup, n-pentylsulfamoyl group, isopentylsulfamoyl group, andhexylsulfamoyl group, preferably a C₁₋₁₀ alkyl group, and morepreferably a C₁₋₆ alkyl group.

Examples of the dialkylsulfamoyl group include sulfamoyl that isdi-substituted with a C₁₋₂₀ alkyl group such as dimethylsulfamoyl group,diethylsulfamoyl group, di-n-propylsulfamoyl group, diisopropylsulfamoylgroup, di-n-butylsulfamoyl group, diisobutylsulfamoyl group,di-tert-butylsulfamoyl group, di-n-pentylsulfamoyl group,diisopentylsulfamoyl group, and dihexylsulfamoyl group, preferably aC₁₋₁₀ alkyl group, and more preferably a C₁₋₆ alkyl group.

“Aryl group” refers to a monocyclic or polycyclic group including afive- or six-membered aromatic hydrocarbon ring, and specific examplesthereof include phenyl group, naphthyl group, fluorenyl group, anthrylgroup, biphenylyl group, tetrahydronaphthyl group,2,3-dihydro-1,4-dioxanaphthalenyl group, indanyl group, indenyl group,indacenyl group, pyrenyl group, naphthacenyl group, perylenyl group,chrysenyl group, acenaphthyl group, acenaphthenyl group, and phenanthrylgroup; and these are optionally substituted with 1 to 5 atoms or groupsdefined above.

“Heteroaryl group” refers to a monocyclic or polycyclic group includinga five- or six-membered aromatic ring having 1 to 3 heteroatoms selectedfrom N, O, S, Se, and Si; and when the “heteroaryl group” is polycyclic,at least one ring thereof may be an aromatic ring. Specific examplesthereof include furyl group, thienyl group, selenophene group, pyrrolylgroup, imidazolyl group, pyrazolyl group, oxazolyl group, thiazolylgroup, isoxazolyl group, isothiazolyl group, pyridyl group, pyrazinylgroup, pyrimidinyl group, pyridazinyl group, indolyl group, quinolylgroup, isoquinolyl group, carbazolyl group, chromanyl group, silolegroup, benzo[b]silole group, benzo[b]furyl group, benzo[b]thienyl group,benzo[b]selenophene group, benzoindolyl group, benzoquinolyl group,benzisoquinolyl group, benzocarbazolyl group, benzochromanyl group,benzimidazolyl group, benzopyrazolyl group, benzoxazolyl group,benzothiazolyl group, benzisoxazolyl group, benzisothiazolyl group,dibenzo[b,d]furyl group, dibenzo[b,d]thienyl group, thieno[3,4-b]thienylgroup, thieno[3,2-b]thienyl group, and fluoro[3,2-b]furyl group; andthese are optionally substituted with 1 to 5 atoms or groups definedabove.

Examples of monoarylamino groups include monoarylamino groups whose arylgroup is as defined above.

Examples of monoheteroarylamino groups include monoheteroarylaminogroups whose heteroaryl group is as defined above.

The “C₁₋₂₀ alkylsulfonyl group” may be linear, branched, or cyclic; andis, for example, a C₁₋₂₀ alkylsulfonyl group such as methylsulfonylgroup, ethylsulfonyl group, n-propylsulfonyl group, isopropylsulfonylgroup, n-butylsulfonyl group, isobutylsulfonyl group, tert-butylsulfonylgroup, n-pentylsulfonyl group, isopentylsulfonyl group, hexylsulfonylgroup, heptylsulfonyl group, octylsulfonyl group, nonylsulfonyl group,decylsulfonyl group, undecylsulfonyl group, dodecylsulfonyl group,tetradecylsulfonyl group, hexadecylsulfonyl group, octadecylsulfonylgroup, and eicosylsulfonyl group, preferably a C₁₋₁₀ alkylsulfonylgroup, and more preferably a C₁₋₆ alkylsulfonyl group.

The “C₁₋₂₀ alkylcarbonylamino group” may be linear, branched, or cyclic;and is, for example a C₁₋₂₀ alkylcarbonylamino group such asmethylcarbonylamino group, ethylcarbonylamino group,n-propylcarbonylamino group, isopropylcarbonylamino group,n-butylcarbonylamino group, isobutylcarbonylamino group,tert-butylcarbonylamino group, n-pentylcarbonylamino group,isopentylcarbonylamino group, hexylcarbonylamino group,heptylcarbonylamino group, octylcarbonylamino group, nonylcarbonylaminogroup, decylcarbonylamino group, undecylcarbonylamino group,dodecylcarbonylamino group, tetradecylcarbonylamino group,hexadecylcarbonylamino group, octadecylcarbonylamino group, andeicosylcarbonylamino group, preferably a C₁₋₁₀ alkylcarbonylamino group,and more preferably a C₁₋₆ alkylcarbonylamino group.

Examples of the C₁₋₂₀ alkoxycarbonylamino group (e.g., a C₁₋₁₂alkoxycarbonylamino group and a C₁₋₆ alkoxycarbonylamino group) includemethoxycarbonylamino group, ethoxycarbonylamino group,propoxycarbonylamino group, isopropoxycarbonylamino group,butoxycarbonylamino group, isobutoxycarbonylamino group,tert-butoxycarbonylamino group, pentyloxycarbonylamino group,isopentyloxycarbonylamino, and hexyloxycarbonylamino.

The C₁₋₂₀ alkylsulfonylamino group (e.g., a C₁₋₁₀ alkylsulfonylaminogroup and a C₁₋₆ alkylsulfonylamino group) is, for example, a C₁₋₁₂alkylsulfonylamino group such as methylsulfonylamino group,ethylsulfonylamino group, n-propylsulfonylamino group,isopropylsulfonylamino group, n-butylsulfonylamino group,isobutylsulfonylamino group, tert-butylsulfonylamino group,n-pentylsulfonylamino group, isopentylsulfonylamino group,hexylsulfonylamino, octylsulfonylamino group, nonylsulfonylamino group,decylsulfonylamino group, undecylsulfonylamino group,dodecylsulfonylamino group, tetradecylsulfonylamino group,hexadecylsulfonylamino group, octadecylsulfonylamino group, andeicosylsulfonylamino group, preferably a C₁₋₁₀ alkylsulfonylamino group,and more preferably a C₁₋₆ alkylsulfonylamino group.

Examples of the C₁₋₂₀ alkoxycarbonyl group (e.g., a C₁₋₁₀ alkoxycarbonylgroup and a C₁₋₆ alkoxycarbonyl group) include methoxycarbonyl group,ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group,butoxycarbonyl group, isobutoxycarbonyl group, tert-butoxycarbonylgroup, pentyloxycarbonyl group, isopentyloxycarbonyl group, andhexyloxycarbonyl group.

Examples of the C₁₋₂₀ alkylcarbonyl group (e.g., a C₁₋₁₀ alkylcarbonylgroup and a C₁₋₆ alkylcarbonyl group) include acetyl group, propionylgroup, butyryl group, pentylcarbonyl group, hexycarbonyl group,heptylcarbonyl group, octylcarbonyl group, nonylcarbonyl group, anddecylcarbonyl group.

Examples of the monoaryl-substituted alkenyl group (e.g., amonoaryl-substituted C₂₋₁₂ alkenyl group and a monoaryl-substituted C₂₋₆alkenyl group) include a monoaryl-substituted alkenyl group whose arylgroup is as defined above, such as styryl group.

Examples of the diaryl-substituted alkenyl group (e.g., adiaryl-substituted C₂₋₁₂ alkenyl group, and a diaryl-substituted C₂₋₆alkenyl group) include a diaryl-substituted alkenyl group whose arylgroup is as defined above, such as diphenylvinyl group.

Examples of the monoheteroaryl-substituted alkenyl group (e.g., amonoheteroaryl-substituted C₂₋₁₂ alkenyl group and amonoheteroaryl-substituted C₂₋₆ alkenyl group) include amonoheteroaryl-substituted alkenyl group whose heteroaryl group is asdefined above, such as thienylvinyl group.

Examples of the diheteroaryl-substituted alkenyl group (e.g., adiheteroaryl-substituted C₂₋₁₂ alkenyl group and adiheteroaryl-substituted C₂₋₆ alkenyl group) include adiheteroaryl-substituted alkenyl group whose heteroaryl group is asdefined above, such as dithienylvinyl group.

Examples of the arylethynyl group include an arylethynyl group whosearyl group is as defined above.

Examples of the heteroarylethynyl group include a heteroarylethynylgroup whose heteroaryl group is as defined above.

Examples of the aryloxy group include an aryloxy group whose aryl groupis as defined above.

R^(a) represents an optionally substituted alkyl group, an optionallysubstituted aryl group, or an optionally substituted heteroaryl group.Examples of “alkyl groups” in the optionally substituted alkyl groupinclude the above-described C₁₋₂₀ alkyl groups, and examples of “arylgroups” in the optionally substituted aryl group includes theabove-described aryl groups. Examples of “heteroaryl groups” in theoptionally substituted heteroaryl group include the above-describedheteroaryl groups.

Next, a method for producing the compound of the present invention willbe described.

The compounds of general formulae (II) and (IIA) of the presentinvention can be synthesized in accordance with the following scheme 1.

It should be noted that the compound in general formula (IIA) isequivalent to the compound in general formula (II) when two R groups oftwo adjacent benzene rings that are bound via N atom represents a singlebond.

(In the formulae, V and X are as defined above.)

Step 1

In the reaction, with respect to 1 mol of the compound of formula (1),about 1 mol to an excessive amount of a base such as alkyl lithiums suchas n-BuLi, Grignard reagents such as n-BuMgBr, alkali metal hydridessuch as NaH and KH, alkali metal alkoxides such as NaO^(t)Bu andKO^(t)Bu, and alkali metal carbonates such as Na₂CO₃, NaHCO₃, K₂CO₃, andCs₂CO₃, and 1 mol to an excessive amount of the compound of formula (2)are used; and Pd(dba)₂ and P^(t)Bu₃ are further used.

The mixture is allowed to react by having it stirred for 30 minutes to24 hours in a solvent at a temperature of −78° C. to about roomtemperature to obtain compound (3).

As the solvent, an anhydrous ether solvent such as anhydrous diethylether, anhydrous THF, or anhydrous dibutyl ether; or an aromatichydrocarbon solvent such as benzene, toluene, xylene, or mesitylene canbe used.

Step 2

Next, compound (3) is deprotonated using a deprotonating agent such asn-BuLi; and a compound including X (a halide, an alkoxy derivative, anaryloxy derivative, an acyloxy derivative, or a haloamino derivative ofX) is added thereto to introduce an X group. Then, by performing aFriedel-Crafts-type reaction in the presence of a Lewis acid such asAlCl₃ and a base such as diisopropylethylamine, the compound of formula(II) can be obtained.

Examples of the compound including X include, when X═P, halides such asPF₃, PCl₃, PBr₃, and PI₃, alkoxy derivatives such as P(OMe)₃, P(OEt)₃,P(O-nPr)₃, P(O-iPr)₃, P(O-nBu)₃, P(O-iBu)₃, P(O-secBu)₃, andP(O-tert-Bu)₃, aryloxy derivatives such as P(OPh)₃ and P(O-naphthyl)₃,acyloxy derivatives such as P(OAc)₃, P(O-trifluoroacetyl)₃,P(O-propionyl)₃, P(O-butyryl)₃, and P(O-benzoyl)₃, and haloaminoderivatives such as PCl(NMe₂)₂, PCl(NEt₂)₂, PCl(NPr₂)₂, PCl(NBu₂)₂,PBr(NMe₂)₂, PBr(NEt₂)₂, PBr(NPr₂)₂, and PBr(NBu₂)₂.

Even when X is other than P (specifically, when X is B, P═O, P═S, P═Se,As, As═O, As═S, As═Se, Sb, Sb═O, Sb═S, Sb═Se, a metal in groups 3 to 11of the periodic table, a metal or metalloid in group 13 or 14 of theperiodic table, or the like), a halide, an alkoxy derivative, an aryloxyderivative, an acyloxy derivative, or a haloamino derivative of X can besimilarly used.

In the reaction, with respect to 1 mol of the compound of formula (3), 1mol to an excessive amount of a deprotonating agent such as n-BuLi, 1mol to an excessive amount of a compound including X, a catalytic amountto an excessive amount of a Lewis acid, and 0 mole to an excessiveamount of a base are used. The mixture is allowed to react by having itstirred for 30 minutes to 24 hours in a solvent at a temperature of −78°C. to about the boiling point of the solvent to obtain the compound offormula (II). As the solvent, an anhydrous ether solvent such asanhydrous diethyl ether, anhydrous THF, or anhydrous dibutyl ether; anaromatic hydrocarbon solvent such as benzene, toluene, xylene, ormesitylene; or an aromatic halide based solvent such as chlorobenzene or1,2-dichlorobenzene can be used. As the deprotonating agent, other thann-BuLi, an alkyl lithium such as MeLi, t-BuLi, or PhLi; a Grignardreagent such as MeMgBr, Et MgBr, or n-BuMgBr; or an alkali metal hydridesuch as NaH or KH can be used. Examples of the Lewis acid that can beused include AlCl₃, AlBr₃, BF₃.OEt₂, BCl₃, BBr₃, GaCl₃, GaBr₃, InCl₃,InBr₃, In(OTf)₃, SnCl₄, SnBr₄, AgOTf, Sc(OTf)₃, ZnCl₂, ZnBr₂, Zn(OTf)₂,MgCl₂, MgBr₂, Mg(OTf)₂, and the like. Examples of the base that can beused include diisopropylethylamine, 2,2,6,6-tetra methyl piperidine,1,2,2,6,6-pentamethylpiperidine, 2,4,6-collidine, 2,6-lutidine,triethylamine, triisobutylamine, and the like. When X═P, a compound inwhich X is P═S can be obtained directly by conducting the reaction thatuses the Lewis acid and the base in the presence of sulfur (S8). Acompound having bound thereto a sulfur atom can also be similarlyobtained when X is other elements such as As and Sb.

In Step 2′, compound (3′) is used instead of compound (3), and thecompound of formula (IIA) can be obtained by performing aFriedel-Crafts-type reaction and a Scholl-type reaction under acondition similar to that in Step 2.

In Step 2″, compound (3″) is used instead of compound (3), and thecompound of formula (IIA) can be obtained by performing aFriedel-Crafts-type reaction under a condition similar to that in Step2.

The compounds of formulae (III), (IIIA), (IV), and (IVA) can besynthesized in accordance with the following scheme 2.

It should be noted that the compounds in general formulae (IIIA) and(IVA) are equivalent to the compounds in general formulae (III) and (IV)when two R groups of two adjacent benzene rings that are bound via Natom represents a single bond.

Furthermore, the compounds of general formulae (II-1) to (II-54), thecompounds of general formulae (II′) to (XXIII′), the compounds ofgeneral formulae (II′-1) to (XIV′-1A), and the compounds having abackbone of 1 to 149 can be easily synthesized by referring to schemes 1to 8.

(In the formulae, V and X are as defined above.)

In scheme 2, a target compound can be obtained similarly to scheme 1,except for changing compounds used for the reaction. In addition thecompound of formula (IVA) can be obtained in a manner similar to Step 2″in scheme 1 by changing the starting material.

The compound in formulae (V), (VA), (VI), and (VIA) can be synthesizedin accordance with the following scheme 3.

It should be noted that the compounds of general formulae (VA) and (VIA)are equivalent to the compounds in general formulae (V) and (VI) whentwo R groups of two adjacent benzene rings that are bound via N atomrepresents a single bond.

(In the formulae, R and X are as defined above.)

Scheme 3 can be conducted similarly to scheme 1, except for changingcompounds used for the reaction.

The compounds of formulae (VII), (VIIA), (VIII), and (VIIIA) can besynthesized in accordance with the following scheme 4. It should benoted that the compounds in general formulae (VIIA) and (VIIIA) areequivalent to the compounds in general formulae (VII) and (VIII) whentwo R groups of two adjacent benzene rings that are bound via N atomrepresents a single bond.

(In the formulae, V and X are as defined above.)

Scheme 4 can be conducted similarly to scheme 1, except for changingcompounds used for the reaction. Furthermore, the compounds of formulae(VIIA) and (VIIIA) can be obtained in a manner similar to Step 2″ inscheme 1 by changing the starting material.

The compounds of formulae (IX), (IXA), (X), and (XA) can be synthesizedin accordance with the following scheme 5.

It should be noted that the compounds in general formulae (IXA) and (XA)are equivalent to the compounds in general formulae (IX) and (X) whentwo R groups of two adjacent benzene rings that are bound via N atomrepresents a single bond.

(In the formulae, R and X are as defined above.)

Scheme 5 can be conducted similarly to scheme 1 except for changingcompounds used for the reaction. Furthermore, the compounds of formulae(IXA) and (XA) can be obtained in a manner similar to Step 2″ in scheme1 by changing the starting material.

The compounds of formulae (XI) and (XIA) can be synthesized inaccordance with the following scheme 6.

It should be noted that the compound of general formula (XIA) isequivalent to the compound in general formula (XI) when two R groups oftwo adjacent benzene rings that are bound via N atom represents a singlebond.

(In the formulae, R and X are as defined above.)

Scheme 6 can be conducted similarly to scheme 1, except for changingcompounds used for the reaction. Furthermore, the compound of formula(XIA) can be obtained in a manner similar to Step 2″ in scheme 1 bychanging the starting material.

The compounds of formulae (XII) and (XIIA) can be synthesized inaccordance with the following scheme 7. It should be noted that thecompound of general formula (XIIA) is equivalent to the compound ingeneral formula (XII) when two R groups of two adjacent benzene ringsthat are bound via N atom represents a single bond.

(In the formulae, V and X are as defined above.)

Scheme 7 can be conducted similarly to scheme 1, except for changingcompounds used for the reaction. Furthermore, the compound of formula(XIIA) can be obtained in a manner similar to Step 2″ in scheme 1 bychanging the starting material.

The compounds of formulae (XIII), (XIIIA), (XIV), and (XIVA) can besynthesized in accordance with the following scheme 8. It should benoted that the compounds of general formulae (XIIIA) and (XIVA) areequivalent to the compounds of general formulae (XIII) and (XIV) whentwo R groups of two adjacent benzene rings that are bound via N atomrepresents a single bond.

(In the formulae, V and X are as defined above.)

Scheme 8 can be conducted similarly to scheme 1, except for changingcompounds used for the reaction. Furthermore, the compounds of formulae(XIIIA) and (XIVA) can be obtained in a manner similar to Step 2″ inscheme 1 by changing the starting material.

Conversion of P═S, P, and P═O at X can be performed in accordance withthe following scheme 9. Conversion of P═S, P, and P═O can be performedfor other compounds of the present invention in a similar manner.

Next, an organic light-emitting element will be described in detail.

The organic light-emitting element of the present invention includes atleast one pair of electrodes including a positive electrode and anegative electrode, and a layer including at least one layer containingan organic compound sandwiched between the one pair of electrodes,wherein the at least one layer of the layer containing the organiccompound includes at least one type of a compound having a partialstructure represented by general formula (I).

In one preferable embodiment, the organic light-emitting element of thepresent invention may include at least one type of the compound as aluminous layer of the layer containing the organic compound.Furthermore, in the case of an organic light-emitting element in whichthe luminous layer contains two or more compounds of a host and a guest,the host or the guest is preferably the compound described above. Itshould be noted that the guest in the present invention is a compoundthat emits light in response to recombination of a positive hole and anelectron in an luminous area of the organic EL element, and is includedin the substance (host) forming the luminous area.

In another embodiment, since the compound of the present invention hashigh charge mobility, the compound can be blended in a positive holetransportation layer as a positive hole transporting material, and canalso be effectively used in an electron transporting layer as anelectron transporting material.

The contained amount of the compound having the partial structurerepresented by general formula (I) according to the present inventionis, when used as a guest, preferably not higher than 50 wt %, furtherpreferably not lower than 0.1 wt % but not higher than 30 wt %, andparticularly preferably not lower than 0.1 wt % but not higher than 15wt %.

On the other hand, when the compound including the partial structurerepresented by general formula (I) according to the present invention isused as a host compound, the guest that is used is not particularlylimited, and a later-described compound or the like can be appropriatelyused depending on the desired color of emitted light, etc. Furthermore,if necessary, other than the guest, a hole transportation compound, anelectron transporting compound, and the like, can be doped together tobe used.

Although the compound of the present invention may be used exclusivelyin a luminous layer as an organic compound layer, if necessary, thecompound can be used in layers other than the luminous layer, such as,for example, a positive hole injection layer, a positive holetransportation layer, a positive hole barrier layer, an electroninjection layer, an electron transporting layer, and an electronicbarrier layer.

In the organic light-emitting element of the present invention, thecompound having the partial structure represented by general formula (I)is formed between a positive electrode and a negative electrode usingvacuum deposition method or solution coating method. The thickness ofthe organic layer is smaller than 10 μm, and is formed in a thin filmhaving a thickness of preferably not larger than 0.5 μm, and morepreferably not smaller than 0.01 but not larger than 0.5 μm.

In the organic light-emitting element of the present invention, thelayer containing the compound having the partial structure representedby general formula (I) and a layer containing other organic compoundsare generally formed into a thin film through a vacuum deposition methodor a method of applying a coating of a compound dissolved in anappropriate solvent. In particular, when a film is formed using acoating method, the compound can be combined with an appropriate binderresin to be formed into a film.

The binder resin can be selected from a wide range of binding resins;and examples thereof include, but are not limited to, polyvinylcarbazole resin, polycarbonate resin, polyester resin, polyarylateresin, polystyrene resin, acrylic resin, methacrylic resin, butyralresin, polyvinyl acetal resin, diallyl phthalate resin, phenol resin,epoxy resin, silicone resin, polysulfone resin, urea resin, and thelike. Furthermore, these resins may be used singly, or one or more typesthereof may be mixed as a copolymer to be used.

As the positive electrode material, for example, an elemental metal suchas gold, platinum, nickel, palladium, cobalt, selenium, and vanadium, analloy thereof, and metal oxides such as tin oxide, zinc oxide, indiumtin oxide (ITO), and indium zinc oxide can be used. In addition, aconductive polymer such as polyaniline, polypyrrole group,polythiophene, and polyphenylene sulfide can also be used. Theseelectrode substances may be used singly, or in a combination of two ormore.

As the negative electrode material, for example, elemental metals suchas lithium, sodium, potassium, cesium, calcium, magnesium, aluminum,indium, silver, lead, tin, and chromium; and an alloy consisting ofmultiple metals can be used. It is also possible to use a metal oxidesuch as indium tin oxide (ITO). Furthermore, the negative electrode mayhave a single-layer configuration or a multilayered configuration.

The substrate used in the present invention is not particularly limited,and opaque substrates such as metallic substrates and ceramicsubstrates; and transparent substrates such as glass, quartz, andplastic sheets can be used. Furthermore, it is also possible to use acolor filter film, a fluorescent color converting filter film, adielectric reflection film, or the like, as the substrate forcontrolling colored light.

It should be noted that it is possible to provide the created elementwith a sealing layer or a protective layer for the purpose of preventingcontact with oxygen, moisture, and the like. Examples of the protectivelayer include inorganic material films such as diamond thin films, metaloxides, and metal nitrides; polymer films such as fluororesin,polyparaxylene, polyethylene, silicone resins, and polystyrene resins;and photo-curable resins. Furthermore, it is also possible to provide acover using glass, a gas-impermeable film, a metal, or the like, andpackage the element itself using an appropriate sealing resin.

The compound of the present invention can also be used as the organicsemiconductor material, or in a composition for forming an organicsemiconductor layer including the compound of the present invention andan organic solvent.

As the organic solvent, a common organic solvent can be used without anyspecial limitation, and preferable examples thereof that can be usedinclude: alcohols including methyl alcohol, ethyl alcohol, n-propylalcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butylalcohol, isobutyl alcohol, and diacetone alcohol; ketones includingacetone, methyl ethyl ketone, and methyl isobutyl ketone; glycolsincluding ethylene glycol, diethylene glycol, triethylene glycol,propyleneglycol, butylene glycol, hexylene glycol, 1,3-propanediol,1,4-butanediol, 1,2,4-butanetriol, 1,5-pentanediol, 1,2-hexanediol, and1,6-hexanediol; glycol ethers including ethylene glycol monomethyl etherand triethylene glycol monoethyl ether; glycol ether acetates includingpropylene glycol monomethyl ether acetate (PGMEA); acetates includingethyl acetate, butoxyethoxy ethyl acetate, butyl carbitol acetate (BCA),and dihydroterpineol acetate (DHTA); terpineols; trimethyl pentanediolmonoisobutyrate (TEXANOL); dichloroethene (DCE); chlorobenzene; andN-methyl-2-pyrrolidone (NMP). With regard to these organic solvents, asingle type may be used by itself, or a combination of two or more typesmay be used.

The composition preferably includes about 0.1 to 10 wt % of the organicsemiconductor material, and about 90 to 99.9 wt % of an organic solvent.

The present invention further provides an organic semiconductor thinfilm that can be formed using the semiconductor layer-formingcomposition. In this case, the thin film can be formed by coating asubstrate with the semiconductor layer-forming composition of thepresent invention.

The substrate is not particularly limited, as long as it does not hinderthe object of the present invention. Those skilled in the art can selectan appropriate substrate depending on the use application, and examplesthereof include: glass substrates; silicon wafers; ITO glass; quartz;silica coated substrates; alumina coated substrates; and plasticsubstrates such as polyethylene naphthalate, polyethylene terephthalate,polycarbonate, polyvinyl alcohol, polyacrylate, polyimide,polynorbornene, and polyethersulfone.

As the coating method, a common wet process performed at ordinarytemperature can be used without limitations, and examples of those thatcan be used preferably include spin coating, dip coating, roll coating,screen coating, spray coating, spin casting, flow coating, screenprinting, ink-jetting, drop casting, and the like.

Although the organic semiconductor thin film of the present inventionmay have a film thickness of about 300 to 2,000 angstrom, the filmthickness is not limited thereto.

The organic semiconductor thin film according to the present inventioncan be produced using a simple wet process performed at ordinarytemperature, and has excellent electrical characteristics satisfyingboth high charge mobility and low leakage current through improvement inintermolecular packing density. Therefore, the organic semiconductorthin film of the present invention can be applied effectively to variousorganic electronic devices.

The present invention further provides an electrochemical deviceincluding the organic semiconductor thin film as a semiconductor layer.

Examples of the electrochemical device include, but are not necessarilylimited to, organic light-emitting elements, organic thin-filmtransistors, organic thin-film solar cells, polymer memories,capacitors, and the like. In this case, the organic semiconductor thinfilm can be applied in the device through a process commonly known inthe art.

Among these electrochemical devices, the present invention particularlyprovides an organic thin-film transistor. The organic thin-filmtransistor of the present invention may include a substrate, a gateelectrode, an organic insulation layer, a semiconductor layer, andsource/drain electrodes; and, as the semiconductor layer, an organicsemiconductor thin film formed from the organic semiconductor materialaccording to the present invention.

The organic thin-film transistor of the present invention may havegenerally known structures of a bottom-contact type, a top-contact type,or a top-gate type; or may have a modified structure, as long as theobject of the present invention is not hindered.

The substrate of the organic thin-film transistor of the presentinvention is not particularly limited, as long as it is a substrate thatis commonly used. Specific examples thereof that can be used includeglass substrates, silica substrates, and plastic substrates such aspolyethylene naphthalate, polyethylene terephthalate, polycarbonate,polyvinyl alcohol group, polyacrylate, polyimide, polynorbonene, andpolyethersulfone.

As the gate electrode, source and drain electrodes, a metal commonlyused can be applied, and specific examples thereof include, but are notlimited to, gold (Au), silver (Ag), aluminum (Al), nickel (Ni), indiumtin oxide (ITO), molybdenum/tungsten (Mo/W), and the like. Although thethicknesses of the gate electrode, and source and drain electrodes arepreferably in a range of about 500 to 2,000 Å, the thicknesses are notnecessarily limited thereto.

As the insulation layer, an insulator that is commonly used and has alarge dielectric constant can be used; specific examples thereofinclude, but are not limited to, a ferroelectric insulator selected fromthe group consisting of Ba_(0.33)Sr_(0.66)TiO₃ (BST), Al₂O₃, Ta₂O₅,La₂O₅, Y₂O₃, and TiO₂; an inorganic insulator selected from the groupconsisting of PbZr_(0.33)Ti_(0.66)O₃ (PZT), Bi₄Ti₃O₁₂, BaMgF₄,SrBi₂(TaNb)₂O₉, Ba(ZrTi)O₃ (BZT), BaTiO₃, SrTiO₃, Bi₄Ti₃O₁₂, SiO₂,SiN_(x), and AlON; or an organic insulator such as polyimide,benzocyclobutene (BCB), parylene, polyacrylate, polyvinyl alcohol, andpolyvinyl phenol. Although the thickness of such insulation layers ispreferably in the range of about 3000 Å to 1 μm, the thickness is notnecessarily limited thereto.

The present invention further provides an organic thin-film solar cell.

The structure of the organic thin-film solar cell of the presentinvention is not particularly limited as long as there is a portionbetween one pair of electrodes containing the compound. Specificexamples thereof include structures having the following configurationon a stable insulating substrate.

(1) Lower electrode/p-layer/n-layer/upper electrode(2) Lower electrode/buffer layer/p-layer/n-layer/upper electrode(3) Lower electrode/p-layer/n-layer/buffer layer/upper electrode(4) Lower electrode/buffer layer/p-layer/n-layer/buffer layer/upperelectrode(5) Lower electrode/buffer layer/p-layer/i-layer (or a mixed layer ofp-material and n-material)/n-layer/buffer layer/upper electrode(6) Lower electrode/buffer layer/p-layer/n-layer/bufferlayer/intermediate electrode/buffer layer/p-layer/n-layer/bufferlayer/upper electrode(7) Lower electrode/buffer layer/p-layer/i-layer (or a mixed layer ofp-material and n-material)/n-layer/buffer layer/intermediateelectrode/buffer layer/p-layer/i-layer (or a mixed layer of p-materialand n-material)/n-layer/buffer layer/upper electrode

In the organic thin-film solar cell of the present invention, thematerial of the present invention may be included in any member formingthe cell. Furthermore, a member containing the material of the presentinvention may contain other additional components. As members and mixedmaterials not containing the material of the present invention, membersand materials known in the art for usage in organic thin-film solarcells can be used.

Preferably, since the material of the present invention has highmobility, it is suitable as a material used in p-layer/i-layer/n-layer.

Preferably, the material of the present invention is used inp-layer/i-layer/n-layer of the element configurations (2) to (7).

In the following, description of each configuration member will beprovided.

1. Lower Electrode, Upper Electrode

The material of the lower electrode and the upper electrode is notparticularly limited, and a conductive material known in the art can beused. For example, as an electrode that is to be connected to p-layer,tin-doped indium oxide (ITO) and metals such as gold (Au), osmium (Os),and palladium (Pd) can be used; and, as an electrode that is to beconnected to n-layer, metals such as silver (Ag), aluminum (Al), indium(In), calcium (Ca), platinum (Pt), and lithium (Li), two componentmetals such as Mg:Ag, Mg:In, and Al:Li, and the above-illustratedelectrode materials to be connected to p-layer can be used.

It should be noted that, in order to obtain highly efficientphotoelectric transfer characteristics, at least one surface of thesolar cell is preferably sufficiently transparent with respect tosunlight spectra. A transparent electrode is formed using a conductivematerial known in the art with a method such as vapor deposition andsputtering to ensure a predetermined translucency. An electrode of areceiving surface preferably has a light transmittance of 10% or higher.In a preferable configuration of a pair of electrodes, one of theelectrode parts includes a metal having a large work function, and theother includes a metal having a small work function.

2. p-Layer, n-Layer, i-Layer

As the n-material, a compound having a function as an electron acceptoris preferable. Examples thereof include: when the n-material is anorganic compound, fullerene derivatives including C60 and C70, carbonnanotubes, perylene derivatives, polycyclic quinone, quinacridone, andthe like; and, when the n-material is polymer based,CN-poly(phenylene-vinylene), MEH—CN-PPV, —CN group or CF₃ groupcontaining polymers, poly(fluorene) derivatives, and the like. Amaterial having high electron mobility is preferable. A material havingsmall electron affinity is further preferable. When such material havingsmall electron affinity is combined as n-layer, sufficient open-endvoltage can be achieved.

When the n-material is an inorganic compound, examples thereof includeinorganic semiconductor compounds having n-type characteristics.Specific examples thereof include compound semiconductors, dopedsemiconductors such as n-Si, GaAs, CdS, PbS, CdSe, InP, Nb₂O₅, WO₃, andFe₂O₃, and conductive oxides including titanium oxides such as titaniumdioxide (TiO₂), titanium monoxide (TiO), and titanium sesquioxide(Ti₂O₃), zinc oxide (ZnO), and tin oxide (SnO₂). These inorganiccompounds may be used singly, or in a combination of two or more. Atitanium oxide is preferably used, and titanium dioxide is particularlypreferably used.

As the p-material, a compound having a function as a positive holeacceptor is preferable. Examples thereof include: when the p-material isan organic compound, amine compounds represented byN,N′-bis(3-tolyl)-N,N′-diphenylbenzidine (mTPD),N,N′-dinaphthyl-N,N′-diphenylbenzidine (NPD),4,4′,4″-tris(phenyl-3-tolylamino)triphenylamine (MTDATA), and the like,phthalocyanines such as phthalocyanine (Pc), copper phthalocyanine(CuPc), zinc phthalocyanine (ZnPc), and titanyl phthalocyanine (TiOPc),and porphyrins represented by octaethylporphyrin (OEP), platinumoctaethylporphyrin (PtOEP), zinc tetraphenylporphyrin (ZnTPP), and thelike; and, when the p-material is a polymer compound, main chain-typeconjugated polymers such as polyhexylthiophene (P3HT) andmethoxyethylhexyloxy phenylenevinylene (MEHPPV), and side chain-typepolymers represented by polyvinyl carbazole and the like.

When the material of the present invention is used in the i-layer, it ispossible to form the i-layer by mixing the p-layer compound or then-layer compound, or form the i-layer by the material of the presentinvention alone. In this case, any of the compounds illustrated abovemay be used in the p-layer or the n-layer.

3. Buffer Layer

Generally, since an organic thin-film solar cell often has a smalloverall film thickness, yield rate in manufacturing cells is oftenreduced due to short-circuiting between the upper electrode and thelower electrode. This is preferably prevented by laminating a bufferlayer.

As a compound preferable for the buffer layer, a compound havingsufficiently high carrier mobility for not lowering short-circuitcurrent, even with a large film-thickness, is preferable. Examplesthereof include bathocuproine (BCP), and aromatic cyclic anhydrides andthe like represented by NTCDA described in the following when thecompound for the buffer layer is a low-molecular-weight compound. Whenthe compound for the buffer layer is a polymer compound, examplesthereof include conductive polymers known in the art represented bypoly(3,4-ethylenedioxy)thiophene:polystyrene sulfonate (PEDOT:PSS),polyaniline:camphorsulfonic acid (PANI:CSA), and the like.

The buffer layer may also be a layer having a role of preventing anexciton from diffusing to an electrode and becoming deactivated. The useof the buffer layer as an exciton blocking layer in such a manner iseffective in order to achieve high efficiency. An exciton blocking layercan be inserted in both the positive electrode side and the negativeelectrode side. Furthermore, the layer can be provided adjacent to anintermediate layer. Examples of materials having such a role includematerials having a large energy gap, such as BCP.

Other than those described above, as the buffer layer material, theinorganic semiconductor compounds illustrated above as a material of then-layer can be used. As the inorganic semiconductor compound, CdTe,p-Si, SiC, GaAs, NiO, WO₃, MoO₃, V₂O₅, and the like, can be used.

4. Substrate

The substrate preferably has mechanical and thermal strength, andtransparency. Examples thereof include glass substrates and transparentresin films. Examples of transparent resin films include polyethylene,ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer,polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride,polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone,polysulfone, polyethersulfone, tetrafluoroethylene-perfluoroalkyl vinylether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylenecopolymer, tetrafluoroethylene-hexafluoropropylene copolymer,polychlorotrifluoroethylene, polyvinylidene fluoride, polyester,polycarbonate, polyurethane, polyimide, polyether imide, polyimide,polypropylene, and the like.

5. Intermediate Electrode

When an intermediate electrode is placed in a laminated organicthin-film solar cell, it becomes possible to separate each photoelectricconversion unit in the laminated element since an electron-positive holerecombination zone is formed. This layer has a role of preventing theformation of reverse heterojunction between an n-layer in a forwardphotoelectric conversion unit and a p-layer in a backward photoelectricconversion unit. The layer between each of the photoelectric conversionunits provides a zone for recombination of an electron entering from theforward photoelectric conversion unit and a positive hole from thebackward photoelectric conversion unit. Efficient recombination of anelectron entering from the forward photoelectric conversion unit and apositive hole from the backward photoelectric conversion unit isnecessary when it is intended to generate photoinduced electric currentin the laminated element.

The material that forms the electron-positive hole recombination zonecreated by the intermediate electrode is not particularly limited, and amaterial forming the upper electrode and the lower electrode can beused. Preferably, the electron-positive hole recombination zone createdby the intermediate electrode includes a thin metal layer. The metallayer is preferably sufficiently thin and semi-transparent such thatlight can reach (multiple) photoelectric conversion unit(s) in the back.

For this purpose, the thickness of the metal layer is preferably thinnerthan about 20 Å. The thickness of the metal film is particularlypreferably about 5 Å. It is thought that such extremely thin metal film(up to 5 Å) is formed not from a continuous film but from isolated metalnano particles. Surprisingly, although this extremely thin metal layeris not continuous, it is still effective as the electron-positive holerecombination layer. Metals that are preferable to be used for thislayer include Ag, Li, LiF, Al, Ti, and Sn. Silver is a metal that isparticularly preferable for this layer.

In order to form each layer of the laminated organic thin-film solarcell or the organic thin-film solar cell of the present invention, dryfilm-forming methods such as vacuum deposition, sputtering, plasma, andion plating, and wet film-forming methods such as spin coating, dipcoating, casting, roll coating, flow coating, and ink-jetting can beused.

The film thickness of each of the layers is not particularly limited,and is set at an appropriate film thickness. Since exciton diffusionlength of an organic thin film is generally known to be small, when thefilm thickness is overly thick, an exciton becomes deactivated beforereaching a hetero interface of a p-material and an n-material, resultingin low photoelectric conversion efficiency. When the film thickness isoverly thin, a pinhole or the like may be generated and sufficient diodecharacteristics cannot be obtained, resulting in low conversionefficiency. Although an ordinary film thickness in the range of 1 nm to10 μm is suitable, a film thickness in the range of 5 nm to 0.2 μm isfurther preferable.

When a dry film-forming method is to be used, a resistive heating methodknown in the art is preferable. When a mixed layer is to be formed, forexample, a film-forming method by simultaneous vapor deposition frommultiple deposition sources is preferable. Further preferably, thesubstrate temperature is controlled when forming a film.

When a wet film-forming method is to be used, the material forming eachlayer is dissolved or dispersed in an appropriate solvent to prepare aluminescent organic solution and form a thin film. Here, any solvent canbe used. Examples thereof include halogenated hydrocarbon solvents suchas dichloromethane, dichloroethane, chloroform, carbon tetrachloride,tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, andchlorotoluene; ether solvents such as dibutyl ether, tetrahydrofuran,dioxane, and anisole; alcohol solvents such as methanol, ethanol,propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve,ethyl cellosolve, and ethylene glycol; hydrocarbon solvents such asbenzene, toluene, xylene, ethylbenzene, hexane, octane, decane, andtetralin; and ester solvents such as ethyl acetate, butyl acetate, andamyl acetate. Among those described above, a hydrocarbon solvent or anether solvent is preferable. In addition, these solvents may be usedsingly, or as a mixture of two or more. Furthermore, the solvent thatcan be used is not limited to those described above.

In the present invention, for any of the organic thin-film layers of theorganic thin-film solar cell or the laminated organic thin-film solarcell, it is possible to use appropriate additives and resins forimproving film-forming characteristics and preventing pinholes in films.Examples of resins that can be used include insulating resins such aspolystyrene, polycarbonate, polyarylate, polyester, polyamide,polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate,and cellulose, and copolymers thereof; photoconductive resins such aspoly-N-vinylcarbazole and polysilane; and conductive resins such aspolythiophene and polypyrrole.

Furthermore, examples of additives include antioxidants, ultravioletray-absorbing agents, plasticizing agents, and the like.

EXAMPLES

The present invention is explained in further detail by Examples;however, the present invention is not limited thereto.

Example 1 Preparation of 4b-aza-12b-thiophosphadibenzo[g,p]chrysene

A hexane solution (6.13 mL, 1.63 M, 10.0 mmol) of butyllithium was addedto bis(biphenyl-2-yl)amine (3.21 g, 10.0 mmol) and THF (50 mL) at −78°C. under an argon atmosphere, followed by stirring. One hour later,phosphorus trichloride (1.37 g, 10.0 mmol) was added thereto, and themixture was stirred for one hour.

The mixture was warmed to 0° C. and further stirred for one hour. Afterdistilling off the solvent under reduced pressure, 1,2-dichlorobenzene(80 mL) was added thereto.

Thereafter, aluminum trichloride (4.00 g, 30.0 mmol) and sulfur (0.481g, 15.0 mmol) were added thereto, and the mixture was stirred at 120° C.for 18 hours.

1,4-Diazabicyclo[2.2.2.]octane (3.36 g, 30.0 mmol) was added thereto,and the mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound as awhite powder (0.725 g, yield: 19%).

HRMS (EI) m/z; calcd. 381.0741[M]⁺; found 381.0746.

¹H NMR (δppm in CD₂Cl₂ at −40° C.); 6.65 (d, 1H, J=8.4 Hz), 7.01 (t, 1H,J=7.2 Hz), 7.09 (t, 1H, J=7.8 Hz), 7.19 (dd, 1H, J=7.8, 13.8 Hz), 7.31(td, 1H, J=3.0, 7.8 Hz), 7.54 (t, 1H, J=7.8 Hz), 7.62 (d, 1H, J=7.2 Hz),7.65-7.69 (m, 2H), 7.75 (td, 1H, J=3.0, 7.8 Hz), 7.84-7.91 (m, 3H), 8.05(d, 2H, J=7.2 Hz), 8.09 (t, 1H, J=7.2 Hz), 8.58 (dd, 1H, J=7.8, 15.6Hz); ¹³C NMR (δppm in CD₂Cl₂ at −40° C.); 118.1, 120.8, 121.2, 122.3,124.4, 126.5, 128.1, 128.5, 128.6, 128.7, 128.9, 129.3, 130.2 (2C),131.6, 132.1, 132.8, 132.9, 134.4, 134.5, 135.2, 135.3, 136.2, 141.5

Example 2 Preparation of 4b-aza-12b-phenyl-12b-siladibenzo[g,p]chrysene

A hexane solution (0.62 mL, 1.60 M, 1.00 mmol) of butyllithium was addedto bis(biphenyl-2-yl)amine (0.321 g, 1.00 mmol) and tetrahydrofuran (5mL) at −78° C. under an argon atmosphere, followed by stirring. Afterone hour of stirring, phenyl trichlorosilane (0.212 g, 1.00 mmol) wasadded thereto at −78° C., and stirred at room temperature for 12 hours.

After distilling off the solvent under reduced pressure,1,2-dichlorobenzene was added thereto.

Thereafter, aluminum trichloride (0.533 g, 4.00 mmol) and2,2,6,6-tetramethylpiperidine (0.233 g, 1.50 mmol) were added thereto,and the mixture was stirred at 150° C. for 18 hours.

1,4-Diazabicyclo[2.2.2.]octane (0.449 g, 4.00 mmol) was added thereto,and the mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound as awhite powder (0.064 g, yield: 15%). The title compound wasrecrystallized from hexane to obtain a colorless needle crystal, and thestructure was determined by X-ray crystal structure analysis.

HRMS (FAB) m/z; calcd. 423.1443[M]⁺; found 423.1426.

X-Ray Crystal Structure

Example 3 Preparation of 4b-aza-12b-germa-12b-phenyldibenzo[g,p]chrysene

A hexane solution (1.25 mL, 1.60 M, 2.00 mmol) of butyllithium was addedto bis(biphenyl-2-yl)amine (0.643 g, 2.00 mmol) and toluene (80 mL) at−78° C. under an argon atmosphere, followed by stirring. One hour later,the mixture was warmed to 0° C., and further stirred for one hour.Phenyl trichlorogermanium (0.512 g, 2.00 mmol) was then added at −78° C.and stirred at room temperature for 12 hours.

After distilling off the solvent under reduced pressure,1,2-dichlorobenzene was added thereto.

Thereafter, aluminum trichloride (1.07 g, 8.00 mmol) and2,2,6,6-tetramethylpiperidine (0.466 g, 3.00 mmol) were added thereto,and the mixture was stirred at 150° C. for 24 hours.

1,4-Diazabicyclo[2.2.2.]octane (1.12 g, 10.0 mmol) was added thereto,and the mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound as awhite powder (0.389 g, yield: 42%). The title compound wasrecrystallized from hexane to obtain a colorless column crystal, and thestructure was determined by X-ray crystal structure analysis.

HRMS (MALDI) m/z; calcd. 470.0964[M+H]⁺; found 470.0980.

X-Ray Crystal Structure

Example 4 Preparation of 4b-aza-12b-boradibenzo[g,p]chrysene SynthesisExample 1

A hexane solution (9.35 mL, 1.60 M, 15.0 mmol) of butyllithium was addedto bis(biphenyl-2-yl)amine (4.82 g, 15.0 mmol) and toluene (80 mL) at−78° C. under an argon atmosphere, followed by stirring.

One hour later, the mixture was warmed to 0° C. and further stirred forone hour.

A heptane solution (15.0 mL, 1.00 M, 15.0 mmol) of boron trichloride wasadded at −78° C. and stirred at room temperature for 12 hours.

After distilling off the solvent under reduced pressure,1,2-dichlorobenzene was added thereto.

Thereafter, aluminum trichloride (8.00 g, 60.0 mmol) and2,2,6,6-tetramethylpiperidine (3.49 g, 22.5 mmol) were added thereto,and the mixture was stirred at 150° C. for 12 hours.

1,4-Diazabicyclo[2.2.2.]octane (6.73 g, 60.0 mmol) was added thereto,and the mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound as awhitish yellow powder (3.31 g, yield: 67%).

Anal. calcd. for C₂₄H₁₆NB C, 87.56; H, 4.90; N, 4.25. found C, 87.79; H,5.14; N, 4.31.

HRMS (EI) m/z; calcd. 329.1376[M]⁺; found 329.1380.

¹H NMR (δppm in CS₂/CD₂Cl₂=2/1, 600 MHz); 7.26-7.34 (m, 4H, NCCHCHCH),7.55 (td, J=1.2, 7.2 Hz, 2H, BCCHCH), 7.71 (td, J=1.2, 7.2 Hz, 2H,BCCCHCH), 8.04 (dd, J=1.8, 7.8 Hz, 2H, NCCH), 8.28 (dd, J=1.8, 7.8 Hz,2H, NCCCH), 8.33 (d, J=7.8 Hz, 2H, BCCCH), 8.62 (dd, J=1.2, 7.2 Hz, 2H,BCCH); ¹C NMR (δppm in CS₂/CD₂Cl₂=2/1, 151 MHz); 121.3 (2C), 123.1 (2C),123.2 (2C), 125.6 (2C), 126.9 (4C), 127.6 (2C), 131.1 (2C), 132.6 (br,2C, CBC), 135.6 (2C), 137.1 (2C), 138.8 (2C); ¹¹B NMR (δppm inCS₂/CD₂Cl₂=2/1, 193 MHz); 35.6;

Synthesis Example 2

A heptane solution (0.10 mL, 1.00 M, 0.10 mmol) of boron trichloride wasadded to 4b-aza-12b-phenyl-12b-germadibenzo[g,p]chrysene (0.025 g, 0.05mmol) and 1,2-dichlorobenzene (1 mL) at room temperature under an argonatmosphere, followed by stirring at 150° C. for 40 hours.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound as awhitish yellow powder (1.6 mg, yield: 10%).

Example 5 Preparation of 2,7-dibromo-4b-aza-12b-boradibenzo[g,p]chrysene

N-Bromosuccinimide (0.178 g, 1.00 mmol) was added to4b-aza-12b-boradibenzo[g,p]chrysene (0.165 g, 0.50 mmol), methylenechloride (6.0 mL), and acetonitrile (2.0 mL) at room temperature,followed by stirring for one hour.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by GPC to obtain the title compound as a whitishyellow powder (0.228 g, yield: 94%).

Anal. calcd. for C₂₄H₁₄NBBr₂° C., 59.19; H, 2.90; N, 2.88. found C,59.13; H, 3.08; N, 2.93.

¹H NMR (δppm in CDCl₃, 392 MHz); 7.46 (dd, J=2.3, 9.0 Hz, 2H, NCCHCH),7.65 (t, J=7.2 Hz, 2H, BCCHCH), 7.81 (t, J=7.2 Hz, 2H, BCCHCHCH), 7.89(d, J=9.0 Hz, 2H, NCCH), 8.35 (d, J=7.6 Hz, 2H, BCCCH), 8.46 (d, J=2.3Hz, 2H, NCCCH), 8.68 (d, J=7.6 Hz, 2H, BCCH); ¹³C NMR (δppm in CDCl₃,98.5 MHz); 116.2 (2C), 122.8 (2C), 123.1 (2C), 127.6 (2C), 128.3 (2C),129.5 (2C), 129.6 (2C), 131.5 (2C), 135.6 (2C), 135.7 (2C), 137.5 (2C).

Example 6 Preparation of2,7-dimethyl-4b-aza-12b-boradibenzo[g,p]chrysene

A hexane solution (0.63 mL, 1.60 M, 1.00 mmol) of butyllithium was addedto 2,7-dibromo-4b-aza-12b-boradibenzo[g,p]chrysene (0.243 g, 0.50 mmol)and toluene (5.0 mL) at −78° C. under an argon atmosphere, followed bystirring at 40° C. for 24 hours.

Thereafter, methyl iodide (0.178 g, 1.00 mmol) was added thereto, andthe mixture was stirred for one hour.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by GPC to obtain the title compound as a whitishyellow powder (0.228 g, yield: 20%).

HRMS (EI) m/z; calcd. 357.1689[M]⁺; found 357.1692.

¹¹B NMR (δppm in C₆D₆) 34.0.

Example 7 Preparation of14b¹-aza-14b-borabenzo[p]indeno[1,2,3,4-defg]chrysene

A hexane solution (1.23 mL, 1.60 M, 2.00 mmol) of butyllithium was addedto bis(biphenyl-2-yl)amine (0.643 g, 2.00 mmol) and toluene (10 mL) at−78° C. under an argon atmosphere, followed by stirring.

One hour later, the mixture was warmed to 0° C. and further stirred forone hour.

A heptane solution (2.00 mL, 1.00 M, 2.00 mmol) of boron trichloride wasadded at −78° C. and stirred at room temperature for 12 hours.

After distilling off the solvent under reduced pressure,1,2-dichlorobenzene (20 mL) was added thereto. Thereafter, aluminumtrichloride (1.07 g, 8.00 mmol), and ethyldiisopropyl amine (0.258 g,2.00 mmol) were added thereto, and the mixture was stirred at 180° C.for 12 hours.

1,4-Diazabicyclo[2.2.2.]octane (0.896 g, 8.00 mmol) was added thereto,and the mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound as awhitish yellow powder (0.255 g, yield: 39%).

HRMS (EI) m/z; calcd. 327.1219[M]⁺; found 327.1215.

¹H NMR (δppm in CDCl₃); 7.66-7.72 (m, 4H), 7.84 (td, 2H, J=1.4, 8.2 Hz),8.21 (d, 2H, J=7.8 Hz), 8.43 (d, 2H, J=7.8 Hz), 8.67 (d, 2H, J=7.8 Hz),9.18 (d, 2H, J=7.8 Hz).

Example 8 Preparation of6,9-dichloro-14b¹-aza-14b-borabenzo[p]indeno[1,2,3,4-defg]chrysene

A hexane solution (1.56 mL, 1.60 M, 2.50 mmol) of butyllithium was addedto 3,6-dichloro-1,8-diphenyl carbazole (0.971 g, 2.50 mmol) and toluene(10 mL) at −78° C. under an argon atmosphere, followed by stirring.

One hour later, the mixture was warmed to 0° C. and further stirred forone hour.

A heptane solution (2.50 mL, 1.00 M, 2.50 mmol) of boron trichloride wasadded at −78° C. and stirred at room temperature for 12 hours.

After distilling off the solvent under reduced pressure,1,2-dichlorobenzene (50 mL) was added thereto.

Thereafter, aluminum trichloride (1.33 g, 10.0 mmol) was added thereto,and the mixture was stirred at 160° C. for 14 hours.1,4-Diazabicyclo[2.2.2.]octane (1.12 g, 10.0 mmol) was added thereto,and the mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound as ayellowish brown powder (0.297 g, yield: 30%).

HRMS (EI) m/z; calcd. 395.0440[M]⁺; found 395.0426.

Example 9 Preparation of 4b-aza-12b-phosphadibenzo[g,p]chrysene

Chlorobenzene (3.0 mL) was added to4b-aza-12b-thiophosphadibenzo[g,p]chrysene (0.114 g, 0.30 mmol) andtriethylphosphine (0.039 g, 0.33 mmol) at 0° C. under an argonatmosphere, followed by stirring at 120° C. for 18 hours. The substanceobtained by distilling off the solvent under reduced pressure wassubjected to trituration using hexane to obtain the title compound as awhite powder (0.073 g, yield: 70%).

HRMS (EI) m/z; calcd. 349.1020[M]⁺; found 349.1013.

³¹P NMR (δppm in C₆D₆) 12.7.

Example 10 Preparation of 4b-aza-12b-oxa-phosphadibenzo[g,p]chrysene

A 30% hydrogen peroxide solution (2.0 mL) was added to4b-aza-12b-phosphadibenzo[g,p]chrysene (0.070 g, 0.20 mmol) anddichloromethane (2.0 mL), followed by stirring at room temperature for 6hours.

The crude product obtained by distilling off the solvent of theextracted organic layer under reduced pressure was isolated by HPLC andGPC to obtain the title compound as a whitish yellow powder (0.066 g,yield: 90%).

HRMS (ESI) m/z; calcd. 366.1042[M+H]⁺; found 366.1032. ³¹P NMR (δppm inC₆D₆) 6.6.

Example 11 Preparation of8b,19b-diaza-11b,22b-dithio-phosphahexabenzo[a,c,fg,j,l,op]tetracene

A hexane solution (2.45 mL, 1.63 M, 4.0 mmol) of butyllithium was addedto N,N′-bis(biphenyl-2-yl)-2,6-diaminobiphenyl (0.977 g, 2.00 mmol) andtoluene (20 mL) at −78° C. under an argon atmosphere, followed bystirring.

One hour later, phosphorus trichloride (0.549 g, 4.0 mmol) was addedthereto, and the mixture was stirred for one hour.

The mixture was warmed to 0° C. and further stirred for one hour.

After distilling off the solvent under reduced pressure,1,2-dichlorobenzene (40 mL) was added thereto.

Thereafter, aluminum trichloride (2.13 g, 16.0 mmol) and sulfur (0.192g, 6.0 mmol) were added thereto, and the mixture was stirred at 120° C.for 18 hours.

1,4-Diazabicyclo[2.2.2.]octane (1.79 g, 16.0 mmol) was added thereto,and the mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound as awhitish yellow powder (0.122 g, yield: 10%).

HRMS (FAB) m/z; calcd. 609.0778[M+H]⁺; found 609.0762.

Example 12 Preparation of8b,19b-diaza-11b,22b-diborahexabenzo[a,c,fg,j,l,op]tetracene

A hexane solution (2.45 mL, 1.63 M, 4.0 mmol) of butyllithium was addedto N,N′-bis(biphenyl-2-yl)-2,6-diaminobiphenyl (0.977 g, 2.00 mmol) andtoluene (20 mL) at −78° C. under an argon atmosphere, followed bystirring. One hour later, the mixture was warmed to 0° C. and furtherstirred for one hour.

A heptane solution (4.00 mL, 1.00 M, 4.0 mmol) of boron trichloride wasadded at −78° C. and stirred for one hour.

The mixture was warmed to room temperature and further stirred for 12hours.

After distilling off the solvent under reduced pressure,1,2-dichlorobenzene (40 mL) was added thereto.

Thereafter, aluminum trichloride (2.13 g, 16.0 mmol) and (0.192 g, 6.0mmol) were added thereto, and the mixture was stirred at 150° C. for 24hours. 1,4-Diazabicyclo[2.2.2.]octane (1.79 g, 16.0 mmol) was addedthereto, and the mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound as awhitish yellow powder (0.122 g, yield: 40%).

Anal. calcd. for C₃₆H₂₂N₂B₂C, 85.76; H, 4.40; N, 5.56. found C, 85.85;H, 4.24; N, 5.66.

¹H NMR (δppm in CS₂/CD₂Cl₂=2/1, 600 MHz) 7.31-7.34 (m, 4H, NCCCHCH),7.55 (t, J=8.4 Hz, 1H, NCCHCHCHCN), 7.61 (td, J=1.2, 7.2 Hz, 2H,BCCHCHCHCH), 7.78 (td, J=1.2, 7.2 Hz, 2H, BCCHCHCHCH), 7.91 (t, J=7.2Hz, 1H, BCCHCHCHCB), 8.05 (d, J=8.4 Hz, 2H, NCCHCHCHCN), 8.11-8.13 (m,2H, NCCHCHCHCH), 8.32-8.35 (m, 2H, NCCCH), 8.40 (d, J=7.2 Hz, 2H,BCCCH), 8.71 (d, J=7.2 Hz, 2H, BCCHCHCHCH), 8.96 (d, J=7.2 Hz, 2H,BCCHCHCHCB); ¹C NMR (δppm in CS₂/CD₂Cl₂=2/1, 151 MHz) 114.3 (2C), 119.2,121.8 (2C), 123.1 (2C), 123.4 (2C), 125.7, 125.8 (2C), 126.2, 126.7(2C), 127.1 (2C), 128.1 (2C), 130.5 (br, 2C, CBCCCBC), 131.4 (2C), 133.0(br, 2C, CBCCCBC), 135.8 (2C), 137.5 (4C), 137.6 (2C), 138.9, 139.0(2C); ¹¹B NMR (δppm in CS₂/CD₂Cl₂=2/1, 193 MHz) 36.5.

Example 13 Preparation of4b,17b-diaza-9b,22b-diboratetrabenzo[a,c,f,m]phenanthro[9,10-k]tetraphene

A hexane solution (0.62 mL, 1.63 M, 1.0 mmol) of butyllithium was addedto N,N′-bis(biphenyl-2-yl)-2,2″-diamino terphenyl (0.565 g, 1.00 mmol)and toluene (10 mL) at −78° C. under an argon atmosphere, followed bystirring.

One hour later, the mixture was warmed to 0° C. and further stirred forone hour. A heptane solution (1.00 mL, 1.00 M, 1.0 mmol) of borontrichloride was added thereto at −78° C. and the mixture was stirred forone hour.

The mixture was then warmed to room temperature and further stirred for12 hours.

After distilling off the solvent under reduced pressure,1,2-dichlorobenzene (20 mL) was added thereto.

Thereafter, aluminum trichloride (2.13 g, 16.0 mmol) and (0.192 g, 6.0mmol) were added thereto, and the mixture was stirred at 150° C. for 24hours.

1,4-Diazabicyclo[2.2.2.]octane (1.79 g, 16.0 mmol) was added thereto,and the mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound as awhitish yellow powder (0.133 g, yield: 23%).

HRMS (FAB) m/z; calcd. 580.2282[M]⁺; found 580.2296.

¹¹B NMR (δppm in CS₂/C₆D₆=2/1, 126 MHz) 35.7.

Example 14 Preparation of11b-aza-3b-borabenzo[11,12]chryseno[6,5-b]thiophene

A hexane solution (1.25 mL, 1.60 M, 2.00 mmol) of butyllithium was addedto N-[(2-thienyl)phenyl-]-N-(biphenyl-2-yl)amine (0.655 g, 2.00 mmol)and toluene (10 mL) at −78° C. under an argon atmosphere, followed bystirring.

One hour later, the mixture was warmed to 0° C. and further stirred forone hour.

A heptane solution (2.00 mL, 1.00 M, 2.00 mmol) of boron trichloride wasadded at −78° C. and stirred at room temperature for 12 hours.

After distilling off the solvent under reduced pressure,1,2-dichlorobenzene (10 mL) was added thereto.

Thereafter, aluminum trichloride (1.07 g, 8.00 mmol) and2,2,6,6-tetramethylpiperidine (0.621 g, 4.00 mmol) were added thereto,and the mixture was stirred at 150° C. for 24 hours.

1,4-Diazabicyclo[2.2.2.]octane (0.897 g, 8.00 mmol) was added thereto,and the mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound as awhitish yellow powder (0.054 g, yield: 8%).

HRMS (EI) m/z; calcd. 335.0940[M]⁺; found 335.0926.

¹H NMR (δppm in C₆D₆, 392 MHz) 6.92-7.11 (m, 5H), 7.39 (td, J=0.9, 7.6Hz, 1H), 7.50 (td, J=1.8, 7.2 Hz, 1H), 7.91-8.00 (m, 4H), 8.11-8.16 (m,2H), 8.63 (dd, J=0.9, 7.6 Hz, 1H).

Example 15 Preparation of11b-aza-3b-borabenzo[11,12]chryseno[5,6-b]thiophene

A hexane solution (1.25 mL, 1.60 M, 2.00 mmol) of butyllithium was addedto N-[(3-thienyl)phenyl-]-N-(biphenyl-2-yl)amine (0.655 g, 2.00 mmol)and toluene (10 mL) at −78° C. under an argon atmosphere, followed bystirring.

One hour later, the mixture was warmed to 0° C. and further stirred forone hour.

A heptane solution (2.00 mL, 1.00 M, 2.00 mmol) of boron trichloride wasadded at −78° C. and stirred at room temperature for 12 hours.

After distilling off the solvent under reduced pressure,1,2-dichlorobenzene (10 mL) was added thereto.

Thereafter, aluminum trichloride (1.07 g, 8.00 mmol) and2,2,6,6-tetramethylpiperidine (0.621 g, 4.00 mmol) were added thereto,and the mixture was stirred at 150° C. for 24 hours.

1,4-Diazabicyclo[2.2.2.]octane (0.897 g, 8.00 mmol) was added thereto,and the mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound as awhitish yellow powder (0.020 g, yield: 3%).

HRMS (EI) m/z; calcd. 335.0940[M]⁺; found 335.0943.

¹H NMR (δppm in C₆D₆, 392 MHz) 7.00-7.05 (m, 2H), 7.07-7.12 (m, 2H),7.40-7.50 (m, 3H), 7.63 (d, J=4.9 Hz, 1H), 7.94 (dd, J=1.8, 8.1 Hz, 1H),8.03 (dd, J=1.3, 8.5 Hz, 1H), 8.08-8.15 (m, 3H), 8.95 (dd, J=1.4, 7.6Hz, 1H).

Example 16 Preparation of1-methyl-11b-aza-3b-borabenzo[11,12]chryseno[5,6-c]thiophene

A hexane solution (1.25 mL, 1.60 M, 2.00 mmol) of butyllithium was addedto N-[(3-(2-methyl)thienyl)phenyl]-N-(biphenyl-2-yl)amine (0.683 g, 2.00mmol) and toluene (10 mL) at −78° C. under an argon atmosphere, followedby stirring.

One hour later, the mixture was warmed to 0° C. and further stirred forone hour.

A heptane solution (2.00 mL, 1.00 M, 2.00 mmol) of boron trichloride wasadded at −78° C. and stirred at room temperature for 12 hours.

After distilling off the solvent under a reduced pressure,1,2-dichlorobenzene (10 mL) was added thereto.

Thereafter, aluminum trichloride (1.07 g, 8.00 mmol) and2,2,6,6-tetramethylpiperidine (0.621 g, 4.00 mmol) were added thereto,and the mixture was stirred at 150° C. for 18 hours.

1,4-Diazabicyclo[2.2.2.]octane (0.897 g, 8.00 mmol) was added theretoand the mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound as abrown powder (0.035 g, yield: 5%).

HRMS (MALDI) m/z; calcd. 349.1091[M]⁺; found 349.1088.

¹¹B NMR (δppm in C₆D₆, 126 MHz) 32.5.

Example 17 Preparation of3b-aza-11b-borabenzo[11,12]chryseno[6,5-b]thiophene

A hexane solution (1.25 mL, 1.60 M, 2.00 mmol) of butyllithium was addedto N-([1,1′-biphenyl]-2-yl)-2-phenylthiophene-3-amine (0.655 g, 2.00mmol) and toluene (10 mL) at −78° C. under an argon atmosphere, followedby stirring.

One hour later, the mixture was warmed to 0° C. and further stirred foranother hour.

A heptane solution (2.00 mL, 1.00 M, 2.00 mmol) of boron trichloride wasadded at −78° C., and stirred at room temperature for 12 hours.

After distilling off the solvent under a reduced pressure,1,2-dichlorobenzene (10 mL) was added thereto.

Thereafter, aluminum trichloride (1.07 g, 8.00 mmol) and2,2,6,6-tetramethylpiperidine (0.621 g, 4.00 mmol) were added thereto,and the mixture was stirred at 150° C. for 24 hours.

1,4-Diazabicyclo[2.2.2.]octane (0.897 g, 8.0 mmol) was added thereto andthe mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound as awhitish yellow powder (0.030 g, yield: 4%).

HRMS (EI) m/z; calcd. 335.0940[M]⁺; found 335.0929.

¹¹B NMR (δppm in C₆D₆, 126 MHz) 34.5.

Example 18 Preparation of12b-aza-4b-boradibenzo[1,k]pyrrolo[1,2-f]phenanthridine

A hexane solution (1.25 mL, 1.60 M, 2.00 mmol) of butyllithium was addedto N-(2-(1H-pyrrol-1-yl)phenyl)-[1,1′-biphenyl]-2-amine (0.621 g, 2.00mmol) and toluene (10 mL) at −78° C. under an argon atmosphere, followedby stirring.

One hour later, the mixture was warmed to 0° C. and further stirred forone hour.

A heptane solution (2.00 mL, 1.00 M, 2.00 mmol) of boron trichloride wasadded at −78° C. and stirred at room temperature for 12 hours.

After distilling off the solvent under a reduced pressure,1,2-dichlorobenzene (10 mL) was added thereto. Thereafter, aluminumtrichloride (1.07 g, 8.00 mmol) and 2,2,6,6-tetramethylpiperidine (0.466g, 3.00 mmol) were added and stirred at 150° C. for 24 hours.

1,4-Diazabicyclo[2.2.2.]octane (1.12 g, 10.0 mmol) was added thereto andthe mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound as awhite powder (0.023 g, yield: 4%).

HRMS (EI) m/z; calcd. 318.1328[M]⁺; found 318.1324.

¹H NMR (δppm in C₆D₆, 392 MHz) 6.72-6.73 (m, 1H), 6.76-6.80 (m, 1H),6.85-6.89 (m, 1H), 7.01-7.09 (m, 2H), 7.28 (dd, J=1.3, 8.5 Hz, 1H),7.35-7.39 (m, 1H), 7.46-7.51 (m, 2H), 7.55 (dd, J=1.3, 3.6 Hz, 1H), 7.80(dd, J=1.3, 8.5 Hz, 1H), 7.86-7.89 (m, 1H), 8.09-8.13 (m, 2H), 8.71 (dd,J=1.3, 7.6 Hz, 1H).

Example 19 Preparation of4b-aza-12b-borabenzo[f]phenanthro[9,10-h]quinoline

A hexane solution (1.25 mL, 1.60 M, 2.00 mmol) of butyllithium was addedto N-([1,1′-biphenyl]-2-yl)-3-phenylpyridin-2-amine (0.645 g, 2.00 mmol)and toluene (10 mL) at −78° C. under an argon atmosphere, followed bystirring.

One hour later, the mixture was warmed to 0° C. and further stirred forone hour.

A heptane solution (2.00 mL, 1.00 M, 2.00 mmol) of boron trichloride wasadded at −78° C., and stirred at room temperature for 12 hours.

After distilling off the solvent under a reduced pressure,1,2-dichlorobenzene (10 mL) was added thereto. Thereafter, aluminumtrichloride (1.07 g, 8.00 mmol) and 2,2,6,6-tetramethylpiperidine (0.621g, 4.00 mmol) were added thereto and stirred at 150° C. for 24 hours.

1,4-Diazabicyclo[2.2.2.]octane (0.897 g, 8.0 mmol) was added thereto andthe mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound.

Example 20 Preparation of4b-aza-12b-phenyl-12b-stannadibenzo[g,p]chrysene

A hexane solution (0.63 mL, 1.60 M, 1.00 mmol) of butyllithium was addedto bis(biphenyl-2-yl)amine (0.321 g, 1.00 mmol) and THF (10 mL) at −78°C. under an argon atmosphere, followed by stirring.

One hour later, phenyltrichlorostannane (0.302 g, 1.00 mmol) was addedat −78° C. and stirred for one hour.

The mixture was further stirred at room temperature for 12 hours. Afterdistilling off the solvent under a reduced pressure, 1,2-dichlorobenzenewas added thereto.

Thereafter, aluminum trichloride (0.533 g, 4.00 mmol) and2,2,6,6-tetramethylpiperidine (0.232 g, 1.50 mmol) were added thereto,and the mixture was stirred at 150° C. for 12 hours.

1,4-Diazabicyclo[2.2.2.]octane (0.448 g, 4.00 mmol) was added theretoand the mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound.

Example 21 Preparation of6c-aza-16b-boradibenzo[c,p]naphtho[1,2-g]chrysene

A hexane solution (8.75 mL, 1.60 M, 14.0 mmol) of butyllithium was addedto bis(2-phenylnaphthalen-1-yl)amine (5.91 g, 14.0 mmol) and toluene (70mL) at −78° C. under an argon atmosphere, followed by stirring. Fiveminutes later, the mixture was warmed to 0° C. and further stirred for 2and a half hours.

Thereafter, a heptane solution (14.0 mL, 1.00 M, 14.0 mmol) of borontrichloride was added at −78° C. and stirred at room temperature for 12hours.

After distilling off the solvent under a reduced pressure,1,2-dichlorobenzene was added thereto.

Thereafter, aluminum trichloride (14.9 g, 112 mmol) and2,2,6,6-tetramethylpiperidine (9.53 mL, 56.0 mmol) were added theretoand the mixture was stirred at 150° C. for 12 hours.

1,4-Diazabicyclo[2.2.2.]octane (12.6 g, 112 mmol) was added thereto andthe mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by washing with hexane to obtain the titlecompound as a brown powder (4.27 g, yield: 68%).

HRMS (EI) m/z; calcd. 429.1694[M]⁺; found 429.1698.

¹H NMR (δppm in CDCl₃); 6.65-6.69 (m, 2H), 7.11 (t, 2H, J=7.4 Hz), 7.16(d, 2H, J=8.9 Hz), 7.64-7.70 (m, 4H), 7.79 (d, 2H, J=8.9 Hz), 7.86 (dd,2H, J=0.9, 7.6 Hz), 8.48 (d, 2H, J=8.9 Hz), 8.60 (d, 2H, J=8.1 Hz), 8.84(d, 2H, J=7.1 Hz).

Example 22 Preparation of 6c-aza-14b-boratribenzo[c,g,p]chrysene

A hexane solution (0.940 mL, 1.60 M, 1.50 mmol) of butyllithium wasadded to N-([1,1′-biphenyl]-2-yl)-2-phenylnaphthalen-1-amine (0.559 g,1.51 mmol) and toluene (7.5 mL) at −78° C. under an argon atmosphere,followed by stirring.

Ten minutes later, the mixture was warmed to 0° C. and further stirredfor one and a half hours.

A heptane solution (1.50 mL, 1.00 M, 1.50 mmol) of boron trichloride wasadded at −78° C. and stirred at room temperature for 12 hours.

After distilling off the solvent under a reduced pressure,1,2-dichlorobenzene was added. Thereafter, aluminum trichloride (0.800g, 6.00 mmol) and 2,2,6,6-tetramethylpiperidine (0.510 mL, 3.00 mmol)were added and the mixture was stirred at 150° C. for 12 hours.

1,4-Diazabicyclo[2.2.2.]octane (0.675 g, 6.01 mmol) was added theretoand the mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by GPC to obtain the title compound as a brownpowder (0.132 g, yield: 23%).

HRMS (EI) m/z; calcd. 379.1532[M]⁺; found 379.1521.

¹H NMR (δppm in CDCl₃); 7.04-7.06 (m, 2H), 7.10-7.15 (m, 1H), 7.18-7.22(m, 1H), 7.37-7.41 (m, 1H), 7.58-7.62 (m, 2H), 7.63-7.67 (m, 1H),7.77-7.89 (m, 4H), 8.30 (d, 1H, J=7.6 Hz), 8.44 (d, 1H, J=8.5 Hz), 8.46(d, 1H, J=8.0 Hz), 8.51 (d, 1H, J=8.0 Hz), 8.74-8.77 (m, 2H).

Example 23 Preparation of 4b-aza-14b-boratribenzo[a,c,f]tetraphene

A hexane solution (0.625 mL, 1.60 M, 1.00 mmol) of butyllithium wasadded to N-(2-(naphthalen-2-yl)phenyl)-[1,1′-biphenyl]-2-amine (0.370 g,0.996 mmol) and toluene (5.0 mL) at −78° C. under an argon atmosphere,followed by stirring.

Fifteen minutes later, the mixture was warmed to 0° C. and furtherstirred for one and a half hours.

A heptane solution (1.00 mL, 1.00 M, 1.00 mmol) of boron trichloride wasadded at −78° C., and the mixture was stirred at room temperature for 12hours.

After distilling off the solvent under a reduced pressure,1,2-dichlorobenzene was added thereto. Thereafter, aluminum trichloride(1.07 g, 8.00 mmol) and 2,2,6,6-tetramethylpiperidine (0.680 mL, 4.00mmol) were added thereto, and the mixture was stirred at 150° C. for 12hours.

1,4-Diazabicyclo[2.2.2.]octane (0.897 g, 8.00 mmol) was added theretoand the mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by GPC to obtain the title compound as a brownpowder (0.219 g, yield: 55%).

HRMS (EI) m/z; calcd. 379.1532[M]⁺; found 379.1538.

¹H NMR (δppm in CDCl₃); 7.26-7.38 (m, 4H), 7.49-7.53 (m, 1H), 7.54-7.60(m, 1H), 7.61-7.65 (m, 1H), 7.75-7.79 (m, 1H), 7.97-8.07 (m, 4H), 8.32(dd, 1H, J=1.6, 7.8 Hz), 8.38-8.43 (m, 2H), 8.73 (s, 1H), 8.78 (dd, 1H,J=1.4, 7.6 Hz), 9.10 (s, 1H).

Example 24 Preparation of2,11-dibromo-6c-aza-16b-boradibenzo[c,p]naphtho[1,2-g]chrysene

N-Bromosuccinimide (0.0444 g, 0.249 mmol) was added to6c-aza-16b-boradibenzo[c,p]naphtho[1,2-g]chrysene (0.0427 g, 0.996 mmol)and methylene chloride (1.0 mL) at room temperature, followed bystirring for 6 hours.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by GPC to obtain the title compound as a brownpowder (0.0222 g, yield: 38%).

HRMS (EI) m/z; calcd. 586.9887[M]⁺; found 586.9885.

¹H NMR (δppm in CDCl₃); 6.79 (dt, 2H, J=1.4, 7.7 Hz), 7.19-7.24 (m, 4H),7.70 (t, 2H, J=6.7 Hz), 7.90 (dt, 2H, J=1.3, 7.4 Hz), 8.12 (d, 2H, J=8.5Hz), 8.55 (d, 2H, J=8.1 Hz), 8.80 (s, 2H), 8.84 (d, 2H, J=6.7 Hz).

Example 25 Preparation of8b,11b,14b-triaza-22b,25b,28b-triboraoctabenzo[a,c,fg,jk,n,p,st,wx]hexacene

A hexane solution (3.68 mL, 1.63 M, 6.00 mmol) of butyllithium was addedtoN²-([1,1′-biphenyl]-2-yl)-N⁶-(6-([1,1′-biphenyl]-2-ylamino)-[1,1′-biphenyl]-2-yl)-[1,1′-biphenyl]-2,6-diamine(1.31 g, 2.00 mmol) and toluene (20 mL) at −78° C. under an argonatmosphere, followed by stirring.

One hour later, the mixture was warmed to 0° C. and further stirred forone hour.

A heptane solution (6.00 mL, 1.00 M, 6.00 mmol) of boron trichloride wasadded at −78° C. and stirred at room temperature for 12 hours.

After distilling off the solvent under a reduced pressure,1,2-dichlorobenzene (40 mL) was added thereto. Thereafter, aluminumtrichloride (4.01 g, 30.0 mmol) and 2,2,6,6-tetramethylpiperidine (1.74g, 11.3 mmol) were added thereto and the mixture was stirred at 150° C.for 12 hours.

1,4-Diazabicyclo[2.2.2.]octane (3.36 g, 30.0 mmol) was added thereto andthe mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound.

Example 26 Preparation of9b,22b-diaza-4b,17b-diboratetrabenzo[a,c,f,m]phenanthro[9,10-k]tetraphene

A hexane solution (2.45 mL, 1.63 M, 4.00 mmol) of butyllithium was addedto N²′,N⁵′-di([1,1′-biphenyl]-2-yl)-[1,1′:4′,1″-terphenyl]-2′,5′-diamine(1.13 g, 2.00 mmol) and toluene (20 mL) at −78° C. under an argonatmosphere, followed by stirring. One hour later, the mixture was warmedto 0° C. and further stirred for one hour.

Thereafter, a heptane solution (4.00 mL, 1.00 M, 4.00 mmol) of borontrichloride was added at −78° C., and stirred at room temperature for 12hours.

After distilling off the solvent under a reduced pressure and adding1,2-dichlorobenzene (40 mL), aluminum trichloride (2.67 g, 20.0 mmol)and 2,2,6,6-tetramethylpiperidine (1.16 g, 7.50 mmol) were added theretoand the mixture was stirred at 150° C. for 12 hours.

1,4-Diazabicyclo[2.2.2.]octane (2.24 g, 20.0 mmol) was added thereto andthe mixture was subjected to filtration.

The crude product obtained by distilling off the solvent under reducedpressure was isolated by HPLC and GPC to obtain the title compound.

Example 27 Preparation of2,7-diphenyl-4b-aza-12b-boradibenzo[g,p]chrysene

Toluene (5.0 mL) was added to2,7-dibromo-4b-aza-12b-boradibenzo[g,p]chrysene (0.243 g, 0.50 mmol),phenylboronic acid (0.122 g, 1.00 mmol),tetrakis(triphenylphosphine)palladium (0.023 g, 0.02 mmol), andpotassium phosphate (0.425 g, 2.00 mol) at 0° C. under an argonatmosphere, followed by stirring at room temperature for 12 hours.

After Celite® filtration, the crude product obtained by distilling offthe solvent under reduced pressure was isolated by HPLC and GPC toobtain the title compound.

Example 28 Preparation of bis(biphenyl-2-yl)amine

2-Bromobiphenyl (23.1 g, 0.10 mol) was added to 2-aminobiphenyl (16.9 g,0.10 mol), bis(dibenzylideneacetone)palladium (0.575 g, 1.0 mmol),sodium tert-butoxide (14.4 g, 0.15 mol) and toluene (100 mL) at 0° C.under an argon atmosphere, followed by stirring at room temperature for7 hours.

After Florisil® filtration, the brown oily substance obtained bydistilling off the solvent under reduced pressure was subject totrituration using hexane to obtain the title compound as a white powder(32.1 g, yield: 98%).

¹H NMR (δppm in CDCl₃); 5.79 (s, 1H), 6.92 (t, J=7.2 Hz, 2H), 7.17-7.27(m, 14H), 7.40 (d, 2H, J=8.1 Hz); ¹³C NMR (δppm in CDCl₃) 117.0, 120.8,127.2, 128.1, 128.7, 129.0, 130.6, 132.0, 138.9, 140.1.

Example 29 Measurement of the carrier mobility of4b-aza-12b-boradibenzo[g,p]chrysene

A glass substrate (26 mm×28 mm×0.5 mm, manufactured by Nippon SheetGlass Co., Ltd.) was used as a transparent support substrate.

This transparent support substrate was mounted in the substrate holderof a commercially available vapor deposition apparatus together with ametal mask to obtain a lower aluminum electrode of 2 mm width.

Subsequently, a tungsten vapor deposition boat having aluminum thereonwas set in the vapor deposition apparatus.

The vacuum chamber was decompressed to 5×10⁻³ Pa or lower, and the vapordeposition boat was warmed to form a translucent lower aluminumelectrode in such a manner that its film thickness would become 10 nm.The vapor deposition rate was 0.05 to 1 nm/sec.

Subsequently, a metal mask for forming an organic layer that wasdesigned to cover the lower aluminum electrode was mounted on thesubstrate holder and set in a vapor deposition apparatus together with avapor deposition boat made of molybdenum that held“4b-aza-12b-boradibenzo[g,p]chrysene” therein.

The vacuum chamber was decompressed to 5×10⁻³ Pa or lower and the vapordeposition boat was warmed to deposit“4b-aza-12b-boradibenzo[g,p]chrysene.” Here, the film thickness was 6 μmand the deposition rate was 0.1 to 10 nm/sec.

Subsequently, a metal mask for forming an upper aluminum electrode wasmounted on the substrate holder and it was set in a vapor depositionapparatus together with a vapor deposition boat made of tungsten havingaluminum thereon.

The metal mask was designed so that the overlapping area having theorganic layers of the upper and lower aluminum electrodes therebetweenbecame 4 mm².

The vacuum chamber was decompressed to 5×10⁻² Pa or lower, and the vapordeposition boat was warmed to form an upper electrode having a filmthickness of 50 nm. The deposition rate was 0.05 to 1 nm/sec.

The carrier mobility was measured using a time-of-flight method.

The measurement was performed using a commercially available measurementapparatus (TOF-401, manufactured by Sumitomo Heavy Industries AdvancedMachinery Co., Ltd.).

A nitrogen gas laser was used as the excitation light source.

While applying an appropriate voltage across the upper and the loweraluminum electrodes, light was irradiated from the translucent loweraluminum electrode side, and the transient photocurrent was observed toobtain the mobility.

The procedure for deriving the mobility based on analysis of thetransient photocurrent waveform is disclosed in pp. 69-70 of “Organicelectroluminescence materials and displays” (published by CMC Co.,Ltd.).

The measurement results revealed that when an electric field strength of0.5 MV/cm was applied, “4b-aza-12b-boradibenzo[g,p]chrysene” had anelectron mobility of 2×10⁻³ (cm²/Vsec) and a hole mobility of 4×10⁻⁴(cm²/Vsec).

Example 30 Measurement of mobility in6c-aza-16b-boradibenzo[c,p]naphtho[1,2-g]chrysene

A sample was prepared in the same manner as in Example 29 except that“6c-aza-16b-boradibenzo[c,p]naphtho[1,2-g]chrysene” was used instead of“4b-aza-12b-boradibenzo[g,p]chrysene” and the thickness of the organiclayer deposited became 8.2 μm. The mobility was observed in the samemanner.

The measurement results revealed that when an electric field strength of0.5 MV/cm was applied, the“6c-aza-16b-boradibenzo[c,p]naphtho[1,2-g]chrysene” had a hole mobilityof 4.6×10⁻⁴ (cm²/Vsec).

1. A polycyclic aromatic compound or a salt thereof represented by thefollowing formula (I):

wherein X represents B, P, P═O, P═S, P═Se, As, As═O, As═S, As═Se, Sb,Sb═O, Sb═S, Sb═Se, an optionally substituted metal in groups 3 to 11 inthe periodic table, or an optionally substituted metal or metalloid ingroup 13 or 14 of the periodic table; and ring A, ring B, ring C, andring D are the same or different, and each represents an optionallysubstituted phenyl ring, an optionally substituted phenyl ring fused toan aryl or heteroaryl ring, an optionally substituted heteroaromaticring, or an optionally substituted heteroaromatic ring fused to an arylor heteroaryl ring, wherein at least one of ring A, ring B, ring C, andring D is an optionally substituted heteroaromatic ring, or anoptionally substituted heteroaromatic ring fused to an aryl orheteroaryl ring, wherein the compound represented by formula (I) is nota heterofullerene.
 2. The polycyclic aromatic compound or salt thereofaccording to claim 1, represented by the following formula (II):

wherein Y^(a)s are the same or different, and each represents C— or N;or two adjacent Y^(a)s on the same ring, together with a bondtherebetween, form N—, O, S, or Se; and X represents B, P, P═O, P═S,P═Se, As, As═O, As═S, As═Se, Sb, Sb═O, Sb═S, Sb═Se, an optionallysubstituted metal in groups 3 to 11 in the periodic table, or anoptionally substituted metal or metalloid in group 13 or 14 of theperiodic table.
 3. The polycyclic aromatic compound or salt thereofaccording to claim 1, wherein the heteroaromatic ring in ring A, ring B,ring C, or ring D is thiophene, pyrrole, or pyridine.
 4. The polycyclicaromatic compound or salt thereof according to claim 1, represented byany one of the following formulae (II-2) to (II-54):

wherein X represents B, P, P═O, P═S, P═Se, As, As═O, As═S, As═Se, Sb,Sb═O, Sb═S, Sb═Se, an optionally substituted metal in groups 3 to 11 inthe periodic table, or an optionally substituted metal or metalloid ingroup 13 or 14 of the periodic table; and Z represents Se, S, O, or N—.5. The polycyclic aromatic compound or salt thereof according to claim 1represented by the following formula (II′):

wherein Ys are the same or different, and each represents CR or N; ortwo adjacent Ys on the same ring, together with a bond therebetween,form NR, O, S, or Se; X represents B, P, P═O, P═S, P═Se, As, As═O, As═S,As═Se, Sb, Sb═O, Sb═S, Sb═Se, an optionally substituted metal in groups3 to 11 in the periodic table, or an optionally substituted metal ormetalloid in group 13 or 14 of the periodic table; R represents ahydrogen atom, halogen atom, C₁₋₂₀ alkyl group, hydroxy C₁₋₂₀ alkylgroup, trifluoromethyl group, C₂₋₁₂ perfluoroalkyl group, C₃₋₈cycloalkyl group, C₂₋₂₀ alkenyl group, C₂₋₂₀ alkynyl group, mono- ordi-aryl-substituted alkenyl group, mono- or di-heteroaryl-substitutedalkenyl group, arylethynyl group, heteroarylethynyl group, hydroxygroup, C₁₋₂₀ alkoxy group, aryloxy group, trifluoromethoxy group,trifluoroethoxy group, C₂₋₁₂ perfluoroalkoxy group, C₁₋₂₀ alkylcarbonylgroup, C₁₋₂₀ alkylsulfonyl group, cyano group, nitro group, amino group,monoalkylamino group, monoarylamino group, monoheteroarylamino group,carbazole group, C₁₋₂₀ alkoxycarbonylamino group, carbamoyl group, mono-or di-alkylcarbamoyl group, sulfamoyl group, mono- or di-alkylsulfamoylgroup, C₁₋₂₀ alkylsulfonylamino group, C₁₋₂₀ alkylcarbonylamino group,aryl group, heteroaryl group, C₁₋₂₀ alkoxycarbonyl group, carboxylgroup, 5-tetrazolyl group, sulfo group (—SO₂OH), fluorosulfonyl group,SR^(a), N(R^(a))₂, B(R^(a))₂, Si(R^(a))₃, or —C≡C—Si(R^(a))₃, (whereinR^(a) represents an optionally substituted alkyl group, an optionallysubstituted aryl group, or an optionally substituted heteroaryl group;or two R^(a)s, together with an atom bound thereto, may form a bicyclicgroup or a tricyclic group optionally having a heteroatom); providethat, the alkyl group, alkenyl group, alkynyl group, and alkoxy groupare each optionally substituted with 1 to 3 atoms or groups, selectedfrom the group consisting of halogen atom, hydroxy group, C₁₋₂₀ alkoxygroup, aryloxy group, amino group, carbazole group, N(R^(a))₂ (whereinR^(a) is as defined above), trifluoromethyl group, C₂₋₁₂ perfluoroalkylgroup, C₃₋₈ cycloalkyl group, aryl group, and heteroaryl group; and thearyl group, aryl moiety, heteroaryl group, heteroaryl moiety, andcarbazole group are each optionally substituted with 1 to 5 atoms orgroups, selected from the group consisting of halogen atom, C₁₋₂₀ alkylgroup, hydroxy C₁₋₂₀ alkyl group, trifluoromethyl group, C₂₋₁₂perfluoroalkyl group, C₃₋₈ cycloalkyl group, C₂₋₂₀ alkenyl group, C₂₋₂₀alkynyl group, mono- or di-aryl-substituted alkenyl group, mono- ordi-heteroaryl-substituted alkenyl group, arylethynyl group,heteroarylethynyl group, hydroxy group, C₁₋₂₀ alkoxy group, aryloxygroup, trifluoromethoxy group, trifluoroethoxy group, C₂₋₁₂perfluoroalkoxy group, cyano group, nitro group, amino group, carbazolegroup, monoalkylamino group, monoarylamino group, monoheteroarylaminogroup, N(R^(a))₂ (wherein R^(a) is as defined above), carbamoyl group,mono- or di-alkylcarbamoyl group, sulfamoyl group, mono- ordi-alkylsulfamoyl group, C₁₋₂₀ alkylcarbonyl group, C₁₋₂₀ alkylsulfonylgroup, C₁₋₂₀ alkylsulfonylamino group, C₁₋₂₀ alkylcarbonylamino group,methylenedioxy group, heteroaryl group, and aryl group, (wherein thearyl group is optionally substituted with 1 to 5 atoms or groups,selected from the group consisting of halogen atom, C₁₋₂₀ alkyl group,C₃₋₈ cycloalkyl group, C₂₋₂₀ alkenyl group, C₂₋₂₀ alkynyl group, hydroxygroup, trifluoromethyl group, C₂₋₁₂ perfluoroalkyl group, C₁₋₂₀ alkoxygroup, aryloxy group, trifluoromethoxy group, trifluoroethoxy group,C₂₋₁₂ perfluoroalkoxy group, C₁₋₂₀ alkylcarbonyl group, C₁₋₂₀alkylsulfonyl group, methylenedioxy group, cyano group, nitro group,amino group, carbazole group, and N(R^(a))₂ (wherein R^(a) is as definedabove)); or, two adjacent Rs on the same ring, together with a carbonatom bound thereto, form a five- or six-membered monocyclic aromaticgroup, bicyclic aromatic group, or tricyclic aromatic group optionallyhaving a heteroatom; or three adjacent Rs on the same ring, togetherwith a carbon atom bound thereto, form a bicyclic aromatic group or atricyclic group optionally having a heteroatom.
 6. (canceled)
 7. Thepolycyclic aromatic compound or salt thereof according to claim 1represented by the following formulae (III′) to (XXIII′):

wherein Ys are the same or different, and each represents CR or N; ortwo adjacent Ys on the same ring, together with a bond therebetween,form NR, O, S, or Se; X represents B, P, P═O, P═S, P═Se, As, As═O, As═S,As═Se, Sb, Sb═O, Sb═S, Sb═Se, an optionally substituted metal in groups3 to 11 in the periodic table, or an optionally substituted metal ormetalloid in group 13 or 14 of the periodic table; and R represents ahydrogen atom, halogen atom, C₁₋₂₀ alkyl group, hydroxy C₁₋₂₀ alkylgroup, trifluoromethyl group, C₂₋₁₂ perfluoroalkyl group, C₃₋₈cycloalkyl group, C₂₋₂₀ alkenyl group, C₂₋₂₀ alkynyl group, mono- ordi-aryl-substituted alkenyl group, mono- or di-heteroaryl-substitutedalkenyl group, arylethynyl group, heteroarylethynyl group, hydroxygroup, C₁₋₂₀ alkoxy group, aryloxy group, trifluoromethoxy group,trifluoroethoxy group, C₂₋₁₂ perfluoroalkoxy group, C₁₋₂₀ alkylcarbonylgroup, C₁₋₂₀ alkylsulfonyl group, cyano group, nitro group, amino group,monoalkylamino group, monoarylamino group, monoheteroarylamino group,carbazole group, C₁₋₂₀ alkoxycarbonylamino group, carbamoyl group, mono-or di-alkylcarbamoyl group, sulfamoyl group, mono- or di-alkylsulfamoylgroup, C₁₋₂₀ alkylsulfonylamino group, C₁₋₂₀ alkylcarbonylamino group,aryl group, heteroaryl group, C₁₋₂₀ alkoxycarbonyl group, carboxylgroup, 5-tetrazolyl group, sulfo group (—SO₂OH), fluorosulfonyl group,SR^(a), N(R^(a))₂, B(R^(a))₂, Si(R^(a))₃, or —C≡C—Si(R^(a))₃ (whereinR^(a) represents an optionally substituted alkyl group, an optionallysubstituted aryl group, or an optionally substituted heteroaryl group;or two R^(a)s, together with an atom bound thereto, may form a bicyclicgroup or a tricyclic group optionally having a heteroatom); providedthat, the alkyl group, the alkenyl group, the alkynyl group, and thealkoxy group are each optionally substituted with 1 to 3 atoms orgroups, selected from the group consisting of halogen atom, hydroxygroup, C₁₋₂₀ alkoxy group, aryloxy group, amino group, carbazole group,N(R^(a))₂ (wherein R^(a) is as defined above), trifluoromethyl group,C₂₋₁₂ perfluoroalkyl group, C₃₋₈ cycloalkyl group, aryl group, andheteroaryl group; and the aryl group, aryl moiety, heteroaryl group,heteroaryl moiety, and carbazole group are each optionally substitutedwith 1 to 5 atoms or groups, selected from the group consisting ofhalogen atom, C₁₋₂₀ alkyl group, hydroxy C₁₋₂₀ alkyl group,trifluoromethyl group, C₂₋₁₂ perfluoroalkyl group, C₃₋₈ cycloalkylgroup, C₂₋₂₀ alkenyl group, C₂₋₂₀ alkynyl group, mono- ordi-aryl-substituted alkenyl group, mono- or di-heteroaryl-substitutedalkenyl group, arylethynyl group, heteroarylethynyl group, hydroxygroup, C₁₋₂₀ alkoxy group, aryloxy group, trifluoromethoxy group,trifluoroethoxy group, C₂₋₁₂ perfluoroalkoxy group, cyano group, nitrogroup, amino group, carbazole group, monoalkylamino group, monoarylaminogroup, monoheteroarylamino group, N(R^(a))₂ (wherein R^(a) is as definedabove), carbamoyl group, mono- or di-alkylcarbamoyl group, sulfamoylgroup, mono- or di-alkylsulfamoyl group, C₁₋₂₀ alkylcarbonyl group,C₁₋₂₀ alkylsulfonyl group, C₁₋₂₀ alkylsulfonylamino group, C₁₋₂₀alkylcarbonylamino group, methylenedioxy group, heteroaryl group, andaryl group (wherein the aryl group is optionally substituted with 1 to 5atoms or groups, selected from the group consisting of halogen atom,C₁₋₂₀ alkyl group, C₃₋₈ cycloalkyl group, C₂₋₂₀ alkenyl group, C₂₋₂₀alkynyl group, hydroxy group, trifluoromethyl group, C₂₋₁₂perfluoroalkyl group, C₁₋₂₀ alkoxy group, aryloxy group,trifluoromethoxy group, trifluoroethoxy group, C₂₋₁₂ perfluoroalkoxygroup, C₁₋₂₀ alkylcarbonyl group, C₁₋₂₀ alkylsulfonyl group,methylenedioxy group, cyano group, nitro group, amino group, carbazolegroup, and N(R^(a))₂ (wherein R^(a) is as defined above); or, twoadjacent Rs on the same ring, together with a carbon atom bound thereto,form a five- or six-membered monocyclic aromatic group, bicyclicaromatic group, or tricyclic aromatic group optionally having aheteroatom; or three adjacent Rs on the same ring, together with acarbon atom bound thereto, form a bicyclic aromatic group or a tricyclicaromatic group optionally having a heteroatom.
 8. (canceled)
 9. Anelectrochemical device comprising the compound according to claim
 1. 10.The electrochemical device according to claim 9, wherein the device isan organic light-emitting element, an organic thin-film transistor, oran organic thin-film solar cell.